Different morphology CeO₂ was used as a catalyst to catalyse the synthesis of trimethylene carbonate from CO₂ and 1,3?propanediol.The structure and composition of cerium oxides were characterized by SEM, TEM, XPS and XRD. The results showed that the yield of trimethylene carbonate was up to 72.5% at 130 ℃ for 4 h when using the rod?shaped cerium oxide as catalyst and 2?cyanopyridine as dehydrating agent. R?CeO₂ has a higher number of defect sites and an suitable specific surface area, The average particle size is small and it has moderate number of Lewis acidic sites. Based on this, the substrate range was expanded, and the experimental results showed that both five?membered cyclic carbonates and six?membered cyclic carbonates could be obtained in good yields.