The removal of Al from the octahedral layer of montmorillonite by organic acid treatment results in increased microporosity generating a material with different surface features from the virgin clay. The micropores thus generated are found to be responsible for ester to ketone transformation. Various parameters of the newly generated pores such as the pore diameter, pore structure, pore volumes and acidity by pyridine-FTIR were evaluated with respect to ester to ketone formation. The best correlation was found between the volume accessibility factors (VAF) and the ketone yield. The VAF reflects the extent of volume space available around the acid site for the reactant to orient in a specific way for the transformation to occur within the pore to form a specific product. This acid site accessibility aspect was further verified by extending to micropores with large VAF generated by treatment with phenoldisulfonic acid (PDSA).