Chromium complexes supported by tetradentate dianionic imine-thioether-bridged bis(phenol) ligands were prepared and employed in the synthesis of poly(cyclohexene carbonate) via the copolymerization of CO₂ and cyclohexene oxide. The catalytic activity, product selectivity, and kinetic behaviors of these [ONSO]CrIII complexes have been systematically investigated. Results indicate the presence of electron-withdrawing substituents on the ligands to enhance catalytic activity and polymer selectivity. A turnover frequency of 100 h^?1 is observed at a temperature of 110 °C, producing polycarbonate with >60% selectivity