A novel solid support adsorbent for CO2 capture was developed by loading pentaethylenehexamine (PEHA) on commercially available mesoporous molecular sieve MCM-41 using wet impregnation method. MCM-41 samples before and after PEHA loading were characterized by X-ray powder diffraction, N2 adsorption/desorption, thermal gravimetric analysis and scanning electron microscope to investigate the textural and thermo-physical properties. CO2 adsorption performance was evaluated in a fixed bed adsorption system. Results indicated that the structure of MCM-41 was preserved after loading PEHA. Surface area and total pore volume of PEHA loaded MCM-41 decreased with the increase of loading. The working adsorption capacity of CO2 could be significantly improved at 60% of PEHA loading and 75°C. The effect of the height of adsorbent bed was investigated and the best working adsorption capacity for MCM-41-PEHA-60 reached 165mg·(g adsorbent)−1 at 75°C. Adsorption/desorption circle showed that the CO2 working adsorption capacity of MCM-41-PEHA kept stable.