In most cases, the slow CO2 sorption kinetics of water-lean solvents—which include low-volatile organic diluents—are the limiting factor when it comes to post-combustion CO2 capture. This study offers a solution by suggesting the use of catalysts based on nanoporous hypercrosslinked polymers (HCPs) to improve the removal efficiency of water-lean solvents based on diethanolamine (DEA) and to increase CO2 mass transfer. Simple and inexpensive monomers were used to prepare three HCPs: HCP-C, HCP-S, and HCP-B, which stand for benzene, polystyrene, and carbazole, respectively. Blends of DEA and Glycerol (Gly) were used to disperse these polymers. Addition of 0.5 wt% HCP to a solvent mixture of 20% DEA and 30% Gly considerably boosts removal efficiency and increases the amount of CO₂ that can be absorbed until the breakthrough point by as much as 3000%, according to the results. Additionally, various gas flow rates, DEA concentrations, and glycerol concentrations were also investigated to determine the HCP-C catalytic effect on the CO2 absorption. A volumetric overall mass transfer coefficient enhancement of up to 319 % is possible in the investigated ranges when using HCP-C, according to the findings. Moreover, a possible catalytic mechanism was suggested.