Samarium trifluoromethanesulfonate (Sm(OTf) 3) was found to be a novel catalyst for synthesis of diphenyl carbonate (DPC) by transesterification of dimethyl carbonate (DMC) with phenol. The best result was obtained by using Sm(OTf) 3 catalyst. The TON reached 21.8 mol DPC/mol Sm when the reaction was carried out at 190 °C with the molar ratio of phenol-to-DMC 4:1 for 12 h. This catalyst could work in aqueous media and in air, and proved reusable.