The continuous microreactor process for the synthesis of cyclic carbonates by the coupling reaction of epoxide and CO2 was designed, using an intramolecular bifunctional catalyst. The effects of catalyst loading, temperature, pressure, and ratio of CO2 to epoxide on the coupling reaction were investigated. The experimental results show that the epoxide can be efficiently converted to the corresponding cyclic carbonate even at mild conditions (120 °C, 1.5 MPa), lower catalyst concentrations (0.5‰ mol), the conversion rate of epoxide can reach 78% within 30 s. Under the same conditions, the continuous microreactor process exhibited 1.8 times efficiency to that of the traditional tank reaction process. These results indicate that the designed microchannel reaction process can significantly enhance the gas-liquid mixing mass transfer during the reaction. Fluent software was used to simulate the gas-liquid mixing in the microreactor for exploring the effect of different working conditions on the CO2-epoxide mixing. Combined with the analysis of experimental results, it is shown that the gas disturbance plays a key factor in affecting gas-liquid mixing.