​​The biomimicry of carbonic anhydrase as the interaction between zinc and imidazole serves as an inspiration to engineer synthetic systems for CO2 capture and utilization. In this research, we developed a zinc–aminopropylimidazole (Zn–api) complex to achieve CO2 insertion and subsequently catalyze its cycloaddition reaction with a variety of epoxides. We investigated the complexation and carbamation reactions of both the unbound ligand and its zinc complex in aqueous and DMSO solutions. In D2O, the unbound api reacts with CO2 through a 1 : 2 mechanism, forming ammonium carbamate. However, in DMSO-d6, the reaction follows a 1 : 1 pathway and leads to carbamic acid. Interestingly, the Zn–api complex captures CO2 differently depending on the solvent, forming an uncharged species (–NHCO2–Zn) in water and a zwitterionic carbamate (–NH2+Br-–CO2–Zn–Im) in DMSO. To our knowledge, a first time zwitterionic carbamate coordination mode via CO2 insertion is verified by in situ ATR-FTIR with a peak centered at 1704 cm-1 and further supported by quantum chemical calculations. The latter complex exhibits excellent catalytic performance for cyclic carbonates synthesis, achieving 94% and 96% conversion for epichlorohydrin carbonate and glycidol carbonate, respectively, under ambient reaction conditions using a CO2 balloon. Notably, it demonstrates remarkable stability over five consecutive catalytic cycles for the ​​coupling of epichlorohydrin and CO2 without a discernible decrease in activity.​