Oxy-fuel combustion is one of the most promising methods for CO₂ capture and storage (CCS) but the operating costs—mainly due to the need for oxygen production—usually lead to an obvious decrease in power generation efficiency. An “oxy-enrich combustion” process was proposed in this study to improve the efficiency of the oxy-fuel combustion process. The oxidizer for oxy-enrich combustion was composed of pure oxygen, air and recycled flue gas. Thus, the CO₂ concentration in the flue gas decreased to 30⁻40%. The PSA (pressure swing adsorption), which has been widely used for CO₂ removal from the shifting gases of ammonia synthesis in China, was applied to capture CO₂ during oxy-enrich combustion. The technological economics of oxy-enrich combustion with PSA was calculated and compared to that of oxy-fuel combustion. The results indicated that, compared with oxy-fuel combustion: (1) the oxy-enrich combustion has fewer capital and operating costs for the ASU (air separation unit) and the recycle fan; (2) there were fewer changes in the components of the flue gas in a furnace for oxy-enrich combustion between dry and wet flue gas circulation; and (3) as the volume ratio of air and oxygen was 2 or 3, the economics of oxy-enrich combustion with PSA were more advantageous.