Esterification of acetic, propanoic and pentanoic acid with methanol, ethanol, 1-propanol, 2-propanol, butanol and 2-butanol was studied in the presence of a fibrous polymer-supported sulphonic acid catalyst, Smopex-101. The reaction temperature in the experiments was 60 °C. Comparative experiments were carried out on an ion-exchange resin, Amberlyst 15 and with a homogeneous catalyst, liquid HCl. The effect of different molar ratios between the reactants (acid and alcohol) on the reaction rate was investigated. The rate constants were related to the substituent effects of the reacting molecules according to the Taft equation. The substituent effects of alcohols were found to follow the Taft relationship, which was not the case for the acids. The experimental results were modelled according to a simple second-order model and a more advanced adsorption-based model. The adsorption-based model, which includes the adsorption of carboxylic acid and water and is consistent with structure-activity relationship, was superior to the second-order model.