The transesterification of dimethyl oxalate (DMO) with phenol to produce methyl phenyl oxalate (MPO) and diphenyl oxalate (DPO) was carried out over TiO2/SiO2 catalyst. The evaluation results showed that TiO2/SiO2 had better activity and excellent selectivity to target products compared with many conventional ester exchange catalysts. The total selectivity to MPO and DPO kept about 99.0% over TiO2/SiO2 and the conversion of DMO was 66.7% at 10% Ti loading, which was the maximum at different Ti loading. The structure and the chemical state of titanium species in TiO2/SiO2 had been investigated by XRD and XPS. The surface Ti(Ⅳ) species in the form of a monolayer was dominant until 6% Ti loading, while crystalline TiO2 was detected at 8% Ti loading. IR of adsorbed pyridine and NH3-TPD characterization indicated that the desirable catalytic activity of TiO2/SiO2 could be ascribed to its weak Lewis acid. Lewis acid sites cooperated with TiO2 to catalyze the synthesis of MPO and DPO.