CuFe-Hydrotalcite-Like Compounds (CuFe-HTLcs) were synthesized by coprecipitation with Cu(NO3)2·6H2O, Fe(NO3)3·9H2O, NaOH and Na2CO3 solution. The sample with Cu2+ / Fe3+ = 2 was of the highest crystalline characterized by XRD and particle size distribution. The synthesis of propylene carbonate from 1,2-propanediol (PG) and urea was performed to evaluate the catalytic activities of the CuFe-HTLcs. The effects of reaction time, temperature, dosage of catalyst on the synthesis of propylene carbonate were fully discussed. The optimal reaction conditions were determined by using orthogonal test design: reaction temperature 170 °C, dosage of catalyst 0.2 g, and molar ratio of PG to urea 2:1, reaction time 3 h. Under the optimal conditions, the conversion of urea nearly reached 100 %, and the selectivity of propylene carbonate was up to 90.4%.