The present invention relates to a method of preparing a perm-selective porous membrane and a method of separating gases using the prepared porous membrane. According to the present invention, a membrane is synthesized using a hierarchically structured alumina porous support by a counter diffusion method. During this synthesis, the diffusion rate of metal ions loaded on the porous support is controlled by controlling the pore size of the porous support, and the position at which the membrane is synthesized is controlled by synthesizing the membrane inside the support. This can increase the physical stability of the membrane and make the membrane thicker so as to ensure higher H2/CO2 separation factors.