The reversible reaction of CO₂ with alcohols in the presence of organic bases was successfully developed to be a toolbox for capturing CO₂ into polymerizable α,ω-diene functionalized carbonate monomers with high structural diversity. These are applicable for thiol–ene click and ADMET polymerization to produce new libraries of poly(thioether carbonates) and unsaturated aromatic–aliphatic polycarbonates with high molecular weights and satisfactory thermal properties.