The pore connectivity, pore size distribution and pore spatial distribution of the porous structure of native and silanized silica particles were determined by matching the experimental nitrogen sorption data with the theoretical results obtained from pore network model simulations. The agreement between theory and experiment is found to be good. The results clearly indicate that the deposition of the silane layer to the pore surfaces of the native silica particles produces a silanized silica particle with a mean pore diameter and pore connectivity smaller than that of the native silica particle. Furthermore, the evaluation of the pore diffusivity of ribonuclease under unretained conditions shows that the lower values of the pore connectivity found in the samples of silanized silica particles, when compared with the values of the pore connectivity obtained for the native silica particles, increase the diffusional mass transfer resistance within the porous structure of the silanized silica particles.