Chloro-functionalized mesoporous MCM-41, SBA-15, MCM-48 and KIT-6 were synthesized by co-condensation of 3-chloropropyl-trimethoxy-silane (CPTMS) and rice husk ash sodium silicate solution, which is subsequently grafted with a heterocyclic amine, homopiperazine (HPZ). X-ray powder diffraction and BET analysis of the chloro-functionalized mesoporous silicas confirmed the similarity between their structural properties and those obtained from conventional silica sources. CO2 adsorption studies of all HPZ-grafted mesoporous silicas exhibited 8-10 wt% of adsorption capacity and are found to be selective, recyclable and thermally stable. Here, the CO2 adsorption reaction is via the traditional carbamate mechanism. The presence of both secondary and tertiary amine in HPZ influences the high CO2 adsorption capacity. Hence, these HPZ-grafted mesoporous silicas could contribute to CO2 capture as a green, tunable, selective and efficient sorbent.