We report the preparation of pore expanded and sulfonic acid functionalized mesoporous silica catalysts by using different kinds of swelling agents such as 1,3,5-trimethyl benzene (TMB), n-decane (D), n-tridecane (TD), and n-hexadecane (HD) at two different ratios of swelling agent/surfactant. Non-swelled mesoporous silica catalyst, SBA-15-SO3H, was also prepared for comparison. The performance of the sulfonic acid functionalized solid acid catalysts by using one-pot synthesis procedure was evaluated in terms of their catalytic activity in the esterification of propionic acid with methanol. The catalysts have been characterized by X-ray diffraction to investigate the phase transition between the hexagonally packed arrangement of cylindrical pores and mesocellular silica foams (MCF), and N-2 adsorption/desorption technique in terms of pore size and distributions. It was concluded from the XRD and N-2 adsorption/desorption analyses that hexagonally packed and cylindrical pore structure is maintained only for low ratio of swelling agent/surfactant and the increase of the dimension of a template micelle is accompanied by an increase in structural disruption, which was attributed to the phase transition from highly ordered hexagonal arrangement to mesocellular foam (MCF) phase with large nodded pore structures rather than cylindrical pores. Among the different swelling agents, TMB and D were found to be effective for the increase in pore diameter (up to 8 and 7.8 nm), whereas, TD and HD (6.6 nm) are effective to maintain the ordered X-ray diffraction patterns resulting mesoporous materials without giving enlargement of pore diameter in comparison with TMB and D. Pore expanded catalysts, SBA-15-SO3H-TMB-0.1 and SBA-15-SO3H-D-0.1, exhibit 68 and 43% enhancement in turnover frequency toward propionic acid methanol esterification, respectively, over non :swelled SBA-15-SO3H, despite possessing similar acid strengths. The increased activity especially for SBA-15-SO3H-TM B-0.1 and SBA-15-SO3H-D-0.1 likely reflects the accessibility to the active sulfonic acid sites as well as acidity.