The effects of catalyst matrix porosity composition on the catalytic performance have been studied using sulfonated mesoporous SBA-15 silica. The matrix was sulfonated with three different methods grafting, in situ oxidation, and carbon infiltration. Additionally, unordered sulfonated mesoporous carbon, and the commercial catalysts Amberlite IR-120 and Nafion 117 were tested. The catalytic performance was evaluated in a Fischer esterification using acetic acid and ethanol, as well as in a transesterification of triglycerides (sunflower oil) and ethanol to produce biodiesel. The study shows that for long carbon chains, the effective wetting of the porous catalyst matrix by the reactants is most important for the catalytic efficiency, while for shorter carbon chain, the mass transport of the reagents trough the porous structure is more important. The catalysts were analysed using electron microscopy and physisorption. The study shows that the reactions are faster with carbon infiltrated materials than the silica materials due to a higher concentration of sulfonic groups linked to the carbon. The in situ functionalized SBA-15 is a more efficient catalyst compared to the post grafted one. All the synthesized catalysts outperform the commercial ones in both reactions in terms of conversion. (C) 2017 Elsevier B.V. All rights reserved.