The transesterification of dimethyl oxalate (DMO) with phenol to produce methyl phenyl oxalate (MPO) and diphenyl oxalate (DPO) was carried out over a SnO2/SiO2 catalyst. The evaluation results showed that SnO2/SiO2 had better activity and total selectivity to MPO and DPO than many conventional ester exchange catalysts. Especially, SnO2/SiO2 was in favor of the disproportionation of MPO into DPO compared with TS-1, MoO3/SiO2, and MoO3-SnO2/SiO2 catalysts. The conversion of DMO was 46.7% and the selectivity to DPO was 22.5% at 8% Sn loadings, which was the maximum at different Sn loadings. IR of adsorbed pyridine and NH3-TPD characterization indicated that the desirable catalytic activity of SnO2/SiO2 could be ascribed to its weak Lewis acidity. The structure and chemical state of tin species in SnO2/SiO2 had been investigated by X-ray diffraction. SnO2 active centers dispersed on a SiO2 carrier with a high specific surface area were of benefit to the transesterification.