Amine-oxide materials synthesized starting from small silica particles and porous silica in combination with polyethyleneimine have been prepared by co-condensation. The materials showing different surface areas and porosity were attained for M2 and M3 with low and high surface areas, respectively. In the new porous materials prepared CO2 adsorption capacity is enhanced at higher temperatures. The morphology of the resulting hybrid material influences the catalytic performance of salphenic cobalt catalysts in the CO2/propylene oxide coupling reactions. Depending on the catalytic reaction conditions (catalyst, cocatalyst, CO2 pressure and reaction temperature), high yields of the CO2/propylene oxide-cycloaddition reaction is favored over the copolymerization reaction.