It is very interesting to synthesize high value-added chemicals from CO₂ under mild conditions with low energy consumption. Here, we report that a novel catalyst, Zn(betaine)₂Br₂, can efficiently promote the cycloaddition of CO₂ with epoxides to synthesize cyclic carbonates under ambient conditions (30 °C, 1 atm). DFT calculations provide important insights into the mechanism, particularly the unusual synergistic catalytic action of Zn²⁺, Br⁻ and NR⁴⁺, which is the critical factor for the outstanding performance of Zn(betaine)₂Br₂. The unique features of the catalyst are that it is cheap, green and very easy to prepare.