The application of pressure swing adsorption (PSA) method to CO2 separation from flue gas was examined. The main process was comprised of PSA and a super cold separator. Carbon dioxide, which present in about 10% concentration in flue gas, was initially concentrated by PSA, and then the concentrated CO2 was liquefied by the super cold separator (condenser) up to a concentration of more than 99%. The objectives of this study were (1) to make clear the effect of absorbent on the PSA performance, and (2) to make clear the suitable PSA operation condition with high CO2 concentration and its high recovery. In this study, a zeolite 13 X adsorbent in the PSA system was useful for CO2 separation from artificial flue gas. By optimization of PSA operation conditions, the product from PSA showed a CO2 concentration of ca. 70% and recovery was more than 90%. In addition, the final product of the process showed CO2 concentration of ca. 99% and recovery of ca. 90%, when the off-gas from the condenser was introduced into the inlet of PSA and the operation conditions of the process were optimized.