The permeabilities of amino acids for isolated cuticular membranes of ivy (Hedera helix L.) were measured at different pH. Cuticular permeances were lowest for the zwitterionic form at pH 6, followed by the cationic form at pH 1. Highest permeances were obtained for the anionic form at pH 11. Permeances were not correlated with octanol/water partition coefficients and decreased at a given pH with increasing molar volume of the solute. This finding suggests that permeation takes place in the polar cuticular pathways. The effect of pH on the cuticular transport properties was analysed according to the porous membrane model considering the polyelectrolytic character of the cuticle in terms of porosity, tortuosity, and size selectivity of the aqueous cuticular pathway which is altered by pH. An increase of water content and permeability of the cuticular membrane was caused by the dissociation of weak acidic groups with increasing pH leading to a swelling of the cuticle induced by fixed negative charges. In addition, the pH-dependent size of the hydration shell of the amino acids was identified as a secondary factor explaining the variability of cuticular permeances.