For effective $CO_2$ separation using pore size controlled membrane, silica was deposited in the mesopores of a $gamma$-alumina film by chemical vapor deposition of tetraethoxysilane (TEOS) and phenyl-substituted ethoxysilanes at 773-873K. The membranes prepared with phenyl-substituted ethoxysilanes were calcined to remove the phenyl group and control the pore size. The gas permaselectivity of prepared membranes was evaluated by using $H_2$, $CO_2$ $N_2$, $CH_2$ and $C_3H_8$ single component and a mixture of $CO_2$ and $N_2$. The membranes produced using TEOS contained micropores having permselectivity only to hydrogen, but the phenyl-subsitituted ethoxysilane derived membranes possessed micorpores which are recognizable molecules of $CO_2$, $N_2$ and $CH_4$. In the diphenyl-diethoxysilane-derived membrane, the $CO_2$ permeance and selectivity of $CO_2$/$CH_4$ were $10^{-6} m^3(STP) cdot m^{-2} cdot s^{-1} cdot kPa^{-1}$ and 11, respectively. Therefore, the use of phenyl-substituted ethoxysilane was effective in controlling micropore size for $CO_2$ separation.