The acid sites concentration of silica sulfuric acid was optimized against pore dimensions depending on the intensity of silanol groups as a key for binding modifier molecules. The texturally modified rice husk silica, of determined intensity of silanol groups, was functionalized with different loadings of SO3H groups to produce solid acid catalysts with different concentrations of acid sites and different sizes of the pore systems. The catalysts were employed in trans-esterification of waste-cocking oil. The obtained optimum catalytic activity was attributed to the proper compensation between acid sites intensity and pore dimensions. The estimated TOF for methyl ester production was found to decrease with the increase of SO3H loading on the catalyst surface. The role of compatibility of the reactants phase with the catalyst nature could be validated by the observed much higher activity of sulfonated lignin in the studied esterification reaction than the modified RHS-acid catalysts under study.