A mixture of 20% CO2, 50% CO, 25% H-2, and 5% CH4, which reflects the gas composition from coal gasification, was subjected to vacuum pressure swing adsorption (VPSA) in order to remove CO2 from the gas fuel. Zeolites and activated carbons were used as adsorbents. The performance of the VPSA process was assessed through the CO2 recovery and productivity and the product purity. A strong correlation between the working capacity of an adsorbent expressed on a volumetric basis and the amount of CO2 produced in the VPSA process was found. It was demonstrated that the rinse of an adsorbent with CO2 before evacuation in the VPSA process allows obtaining activated carbons comparable to that of superior adsorbents such as zeolite 13X. CO2 purity of 95% with a 75% recovery were obtained at ambient temperature and pressure of 1.5 bar for KOH-activated carbon with a highly developed narrow microporosity.