A five-step PSA cycle was studied for CO2 separation from CO2-N2 gas mixture in a single column at elevated temperatures using Poly-ethyleneimine (PEI) impregnated mesoporous silica SBA-15 as adsorbent. The PSA cycle study included a strong adsorptive rinse step in which the strongly adsorbed component, i.e., CO2 was used for rinsing the adsorbent bed in order to increase the purity of CO2 product. The study indicates that the adsorbent is regenerable under typical PSA conditions. The productivity of the adsorbent studied for CO2 separation was found to be comparable with commercial zeolite adsorbents as reported in literature.