Organic–inorganic hybrid silica membranes were prepared via a sol–gel process using organoalkoxysilanes with pendant groups. Two kinds of organoalkoxysilanes, methyltriethoxysilane (MTES) and phenyltriethoxysilane (PhTES), were used to investigate the effect of the pendant groups on the gas permeation properties and micropore structures of hybrid silica membranes. The hybrid silica membranes showed relatively low H 2 permeance, and the H 2 permeance decreased with the pendant group size. Moreover, based on pore sizes determined by normalized Knudsen-based permeance (NKP), the hybrid silica membranes showed large pore sizes that increased with the size of the pendant groups. Compared with silica membranes prepared from tetraethoxysilane (TEOS) and 1,2-bis(triethoxysilyl)ethane (BTESE), which have no pendant groups, the large pore sizes of silica membranes derived from MTES and PhTES were not associated with high H 2 permeance. This could be ascribed to the different membrane structures of MTES- and PhTES-derived silica membranes, due to the presence of pendant groups in the silica matrix.