The separation of CO2 from N2 was investigated with an α-alumina membrane impregnated with BaTiO3. It was found that adsorption of CO2 was favorable at high temperatures due to an endothermic interaction between CO2 and the material, promoting mobile CO2 that enhanced CO2 adsorption-desorption rate and surface diffusion. The experimental separation factor of CO2 to N2 was found to be 1.1-1.2 at 100 °C to 500 °C, which is higher than the separation factor limit of 0.8 predicted by Knudsen diffusion. Though the separation factor was low due to pinholes observed in the membrane, this demonstrates the potential of perovskite materials in their selective surface chemistry for CO2 separation.