The post-synthesis procedure for cyclic amine (morpholine and 1-methylpiperazine) modified mesoporous MCM-48 and SBA-15 silicas was developed. The procedure for preparation of the modified mesoporous materials does not affect the structural characteristics of the initial mesoporous silicas strongly. The initial and modified materials were characterized by XRD, N2 physisorption, thermal analysis, and solid-state NMR. The CO2 adsorption of the obtained materials was tested under dynamic and equilibrium conditions. The NMR data revealed the formation of different CO2 adsorbed forms. The materials exhibited high CO2 absorption capacity lying above the benchmark value of 2 mmol/g and stretching out to the outstanding 4.4 mmol/g in the case of 1-methylpiperazin modified MCM-48. The materials are reusable, and their CO2 adsorption capacities are slightly lower in three adsorption/desorption cycles.