TiO2-GO catalysts were prepared by graphene oxide (GO) and then used to catalyze the transesterification of dimethyl carbonate with phenol to diphenyl carbonate. The characterization results of XRD, TEM, XPS and Py-TPD demonstrated that GO could remarkablely improve the dispersion of TiO2, and the electronic effect of GO could change the chemical states of Ti species and promote the formation of the active Ti(Ⅳ) and the scale of medium Lewis acid sites in GO modified catalysts increased significantly. Consquently, the amount of active sites increased in TiO2-GO which was favorable for the formation of transesterification products. The results indicated that the role of GO in the TiO2-GO catalysts was not just a support, but also an electron promoter. The TiO2-GO 50% catalyst exhibited an excellent catalytic performance for the transesterification of dimethyl carbonate with phenol to diphenyl carbonate. With the the reaction temperature 150~180℃, reaction time 9 h, the 41.8% phenol conversion and 99.9% transesterification selectivity were achieved.