We report the first catalytic application of pore-expanded KIT-6 propylsulfonic acid (PrSO3H) silicas, in fatty acid esterification with methanol under mild conditions. As-synthesized PrSO3H-KIT-6 exhibits a 40 and 70% enhancement in turnover frequency (TOF) toward propanoic and hexanoic acid esterification, respectively, over a PrSO3H-SBA-15 analogue of similar 5 nm pore diameter, reflecting the improved mesopore interconnectivity of KIT-6 over SBA-15. However, pore accessibility becomes rate-limiting in the esterification of longer chain lauric and palmitic acids over both solid acid catalysts. This problem can be overcome via hydrothermal aging protocols which permit expansion of the KIT-6 mesopore to 7 nm, thereby doubling the TOF for lauric and palmitic acid esterification over that achievable with PrSO3H-SBA-15.