The transport phenomena of oxygen and nitrogen across a pure polycar bonate (PC) and CoAlPO4-5/PC membranes were studied. Various CoAlPO4-5 membranes with different cobalt content were added to polycarbonate membranes to improve the gas transport performance. Oxygen and nitrogen isotherms were studied. Solubility of oxygen and nitrogen was greatly increased by adding CoAlPO4-5 to the membranes, which also resulted in a higher solubility ratio of oxygen to nitrogen. It might be that a pinhole of the membrane caused the increase in diffusivity and a decrease in selectivity when excess CoAlPO4-5 was added. The results also showed that CoAlPO4-5 with a higher cobalt content would more effectively increase the gas solubility, but make only a minor change in the solubility ratio of oxygen to nitrogen. It was found that the increase in oxygen to nitrogen selectivity was mainly due to an increased diffusivity ratio of oxygen to nitrogen when CoAlPO4-5 was added into the membranes.