A novel zinc silsesquioxane complex ([(c-C5H9)7Si7O11(OSiMePh2)]2Zn4Me4 (1)) has been used as a model compound for silica-grafted zinc catalysts in the copolymerization of cyclohexene oxide and CO2. Complex 1 exists as a dimer in the solid state and is moderately active in the copolymerization, and polycyclohexene carbonates have been obtained with a carbonate content of 79-98%. Polymerizations with ZnEt2-treated silica particles resulted in polymer particles with n and w values and carbonate contents comparable to those of the polymers obtained with 1. It was further demonstrated that CO2 consumption can be followed online by monitoring the decrease of system pressure during the reaction. CO2 consumption has been interpreted in relation to both polycarbonate and cyclic carbonate formation. These measurements represent the intrinsic kinetics of this reaction, which appear to be directly related to CO2 pressure.