To improve CO2 permselectivity, a modified silica membrane was prepared by chemical vapor deposition with tetraethoxysilane(TEOS)-ethanol-water, and TEOS-ethanol-water-HCI solution at 300-600℃. The silica was effectively deposited in the mesopores of a γ-alumina film coated on a porous α-alumina tube by evacuating the reactants through the porous wall. In this membrane, CO2 interacts, to some extent, with the pore wall, and CO2/N2 selectivity then exceeds the value of the Knudsen diffusion mechanism, while the membrane derived from TEOS alone has no CO2 selectivity. The silica membrane prepared from TEOS-ethanol-water-HC1 solution showed that CO2 permeance was 2.5×10-7㏖/s-1. m-2. Pa-1 at 30℃ and CO2/N2 selectivity was approximately 3. The CO2 permeance and selectivity was improved by enlarging the surface diffusion with modification of chemical affinity of the silica pores.