A　series　of　polymers　are　simply　synthesized　by　the　copolymerization　of　vinyl　functionalized　polyhedral　oligomeric　silsesquioxanes　(POSS)　with　vinylimidazole　based　linker　by　modulating　the　molar　ratio　of　two　monomers.　The　synthesized　POSS-based　polymers　are　capable　of　catalyzing　the　cycloaddition　reaction　of　CO2　with　a　variety　of　epoxides　at　atmospheric　pressure　without　solvent　and　co-catalyst,　producing　cyclic　carbonates　with　conversion　up　to　97.1　%.　Noteworthy,　the　reaction　kinetics　studies　have　demonstrated　that　the　POSS-based　polymers　are　able　to　significantly　reduce　the　activation　energy　of　cycloaddition　reactions　of　CO2.　In　addition,　as　a　heterogenerous　catalysts,　the　POSS-based　polymer　can　be　recovered　and　recycled　5　times　without　reducing　catalytic　performance.