Novel aliphatic polycarbonates with tunable number of cyclic carbonate and epoxide dual functional groups have been synthesized via a (ONSO)CrCl-mediated copolymerization of 4-vinyl-1-cyclohexene diepoxide with carbon dioxide in one pot. The resulting difunctional polycarbonates with high Tg afford a versatile platform for the postpolymerization functionalization.