What Are AHA, BHA, and PHA?

AHA (alpha-hydroxy acids), BHA (beta-hydroxy acid), and PHA (polyhydroxy acids) are the three families of chemical exfoliants. Unlike physical scrubs, they chemically dissolve the bonds between dead skin cells at an acidic pH, enabling controlled desquamation without mechanical abrasion. Van Scott and Yu first documented the clinical potential of AHAs in the 1970s; more than three decades of subsequent research has clarified the mechanisms and safety profiles of all three families.

Molecular Structure and Depth of Action

The most fundamental differences between the three families lie in molecular weight and solubility.

AHA (Alpha-Hydroxy Acids) Water-soluble · Upper epidermis

Molecular weight: small → medium

Glycolic acid · Lactic acid · Mandelic acid

BHA (Beta-Hydroxy Acid) Lipid-soluble · Inside pores

Molecular weight: medium

Salicylic acid — the only acid family that penetrates sebum-filled pores

PHA (Polyhydroxy Acids) Water-soluble · Outermost epidermis

Molecular weight: large

Gluconolactone · Lactobionic acid — minimal irritation, humectant properties

Glycolic acid has the smallest molecular weight among AHAs (76 Da), giving it the deepest epidermal penetration. Salicylic acid is the only lipid-soluble option, allowing it to penetrate pores filled with sebum. Gluconolactone stays near the skin surface due to its large molecular size, making it the gentlest of the three.


AHA (Alpha-Hydroxy Acids)

Mechanism of Action

AHAs work by weakening desmoglein bonds in the lower stratum corneum, reducing cohesion between corneocytes. Tang & Yang (2018) identify two simultaneous pathways:

Immediate Accelerated Desquamation

pH reduction interferes with calcium ion activity in the stratum corneum → weakens intercellular bonds → dissolves the outermost dead skin layer

Long-term Dermal Remodeling

Fibroblast stimulation → increased collagen and hyaluronic acid synthesis → improved skin thickness and elasticity

Clinical Evidence — Ditre et al., 1996

Subjects using glycolic acid cream over 12 months showed histologically confirmed, significant increases in dermal glycosaminoglycan (GAG) density — the first tissue-level evidence that AHAs remodel the dermis, not just the surface.

Key AHA Acids

Glycolic Acid 76 Da · High irritation

OTC 5–15%

Professional peels 20–70%

Strongest keratolytic action, melanin inhibition, and dermal remodeling. Highest photosensitivity — SPF is mandatory.

Lactic Acid 90 Da · Moderate irritation

Typical concentration 5–12%

Exfoliation plus NMF (natural moisturizing factor) production — delivers a dual moisturizing benefit. A gentler alternative to glycolic acid for dry or sensitive skin.

Mandelic Acid 152 Da · Low irritation

Typical concentration 5–10%

Antimicrobial (acne-reducing) and brightening. Larger molecular size slows penetration, minimizing irritation. Lower risk of post-inflammatory hyperpigmentation in deeper skin tones (Fitzpatrick IV–VI).

Clinical Evidence

Clinical Evidence — Sharad, 2013

Meta-analysis confirmed that 20–70% glycolic acid peels produced statistically significant improvements across acne, pigmentation, and photoaging endpoints.

Clinical Evidence — Van Scott & Yu, 1989

AHAs thin the stratum corneum, improving the absorption of subsequently applied moisturizers by over 60%. AHAs function not only as exfoliants but as absorption enhancers for other actives.


BHA (Beta-Hydroxy Acid)

Mechanism of Action

Salicylic acid’s defining property is its lipophilicity. Its structural affinity for sebum allows it to penetrate into sebum-filled pores — dissolving plugs from the inside out. This is fundamentally different from AHAs, which act at the epidermal surface.

Per Arif’s 2015 comprehensive review, salicylic acid operates through four simultaneous pathways:

01 Keratolysis

Disrupts lipid bonds between corneocytes → epidermal exfoliation

02 Comedolysis

Dissolves sebum inside follicular openings → clears blackheads and whiteheads

03 Antimicrobial

Inhibits Cutibacterium acnes proliferation → directly targets the primary acne-causing bacterium

04 Anti-inflammatory

Suppresses the Cox-2 pathway → reduces prostaglandin synthesis → calms acne redness and swelling (same mechanism as aspirin)

Clinical Evidence — Decker & Graber, 2012

2% salicylic acid achieved equivalent reduction in acne lesion count compared to benzoyl peroxide, with significantly less skin dryness reported.

Concentration-Effect Relationship

1

0.5–2%

Toners · serums · moisturizers

Daily pore management, mild exfoliation

2

3–5%

Spot treatments · professional products

Active acne treatment, keratosis

3

10–30%

In-office procedures

Dermatologist-administered chemical peels

When BHA Is the Right Choice

  • Oily, congestion-prone, large-pore skin
  • Recurring blackheads and whiteheads
  • Acne-prone skin (anti-inflammatory co-benefit)
  • Body acne (back, chest)

PHA (Polyhydroxy Acids)

Mechanism of Action

PHAs have higher molecular weights than AHAs and carry multiple hydroxyl (-OH) groups. This structure produces three distinct advantages:

01 Slow Penetration → Minimized Irritation

Large molecular size slows epidermal permeation → suitable for sensitive and atopic skin types

02 Simultaneous Hydration

Multiple hydroxyl groups bind water molecules → exfoliates while actively hydrating the skin

03 Antioxidant

Metal ion chelation → neutralizes free radicals → suppresses oxidative stress

Clinical Evidence — Becker et al., 2012

PHAs showed significantly lower Irritation Index scores than AHAs in sensitive and atopic skin, and were the only acid family confirmed not to worsen transepidermal water loss (TEWL) — a key marker of barrier integrity.

Key PHA Acids

Gluconolactone Antioxidant

Exfoliation combined with potent antioxidant activity via metal chelation. Safe for rosacea and reactive skin types.

Lactobionic Acid Exceptional humectant

Derived from milk sugar (lactose); strongest humectant capacity among PHAs. Ideal for dry, aging, and atopic skin.


Choosing Between AHA, BHA, and PHA

By Skin Type

Oily / Acne-prone BHA → AHA

Salicylic acid (BHA) first — pore purification + anti-inflammation. Glycolic acid (AHA) can be added as a secondary

Dry / Sensitive PHA → Lactic AHA

Minimized irritation with simultaneous hydration benefit

Combination Zone-targeted

BHA on T-zone + AHA on U-zone — targeted care by area

Hyperpigmentation / Photoaging AHA

Glycolic or lactic acid — epidermal renewal + dermal stimulation

Reactive / Atopic PHA

The only acid family confirmed to preserve barrier integrity

Combinations to Avoid

  • AHA/BHA + Retinol · Vitamin A: Concurrent use causes excessive exfoliation and irritation → use in separate routines (AM/PM)
  • AHA/BHA + Vitamin C (L-ascorbic acid): pH conflict may reduce efficacy of both — layer them 20–30 minutes apart
  • AHA/BHA + Niacinamide: High-strength AHAs applied simultaneously may reduce niacinamide efficacy — sequential application is preferred

Ingredient Combination Complete Guide — acid conflict and synergy strategies


Clinical Usage Protocol

Starting with a sensitization-prevention approach is recommended for all new users.

1

Start low

AHA 5% · BHA 0.5–1% · PHA under 10%

2

Begin 1–2× per week

Increase frequency after 4 weeks once tolerance is confirmed

3

Evening use only

AHA/BHA increase photosensitivity — SPF 30+ every morning is non-negotiable

4

Check the pH

Optimal efficacy at pH 3.0–4.0. Keratolytic activity drops sharply above pH 5.

Safety — Green et al., 2009

SPF 50 for at least 2 weeks is recommended after high-concentration AHA peels. Freshly exposed epidermal cells are substantially more vulnerable to UV-induced damage.

FDA OTC Guideline

Maximum AHA concentration of 10% at pH ≥ 3.5 for consumer safety in over-the-counter products.


Multi-Acid Combination Products

An increasing number of products now combine AHA+BHA or AHA+PHA.

Clinical Evidence — Kornhauser et al., 2010

Low-concentration multi-acid formulations achieved comparable exfoliation efficacy to single high-concentration acids, with significantly reduced irritation scores. Component acids must share compatible pH requirements for synergy.

Summary

AHA Water-soluble · upper epidermis — best for photoaging, pigmentation, and overall renewal
BHA Lipid-soluble · penetrates pores — optimal for oily and acne-prone skin
PHA Large molecule · minimal irritation — safest option for sensitive, atopic, and first-time users
SPF Sunscreen after any acid use is not optional — it's clinically mandatory
pH A product must be pH 3.0–4.5 to deliver meaningful exfoliation