Skin-cleansing compositions based on alkyl carboxylates (soaps) have a higher irritation potential than those based on syndet surfactants such as alkyl isethionates or alkyl ether sulphates. Contributing factors include inherent differences in the irritation potential of soaps and syndet surfactants, pH-induced changes in surfactant solution chemistry, and the direct effects of pH on the physical properties of the stratum corneum (SC). Past work has not directly addressed the effect of solution pH on the SC itself and its potential role in cleanser-induced skin irritation. In the current work, alterations to SC properties induced by buffered pH solutions and two strongly ionizable surfactants, sodium dodecyl sulphate and sodium lauryl ether sulphate, at different pH values are measured. By utilizing optical coherence tomography (OCT) and infrared (IR) spectroscopy we have directly measured physical changes in SC proteins and lipids. Our results indicate that SC swelling, which reflects alterations to SC structural proteins, is increased significantly at pH 10, compared to pH 4 and 6.5. The transition temperature (T(m)) of SC lipids is found to increase at pH 10, compared to pH 4 and 6.5, suggesting a more rigid SC lipid matrix. Surfactants cause a further increase in swelling and lipid rigidity. Some aspects of what these results mean for SC physical properties as well as their implications to potential mechanisms of surfactant-induced skin irritation are discussed.