The monolithic materials of reduced graphene oxide (rGO) can be used successfully in CO2 adsorption. Here, the incorporation of CeO2 particles with and without polymer brushes grafted from the particles showed that the structural properties could be changed, affecting the adsorption of CO2. Polymer brushes of (1) poly(acrylic acid) (PAA), (2) poly(vinyl caprolactam) (PVCL) and (3) poly[(2-(methacryloyloxy)ethyl) trimethylammonium chloride] (PMETAC) were grafted from CeO2 via reversible addition−fragmentation chain transfer (RAFT) polymerization. The preparation of monoliths of rGO with different modified CeO2 particles led to different thermal properties (TGA), structural changes (BET isotherms) and CO2 adsorption. The responsive character of the CeO2@polymer was proven by the DLS and UV results. The responsive character of the particles incorporated into the rGO monolith affected not only the adsorption capacity but also the microstructure and values of the surface volume of the pores of the monolith. Monoliths with porosity values for better adsorption were affected by the responsive character of the polymer.