[Display omitted] • TiO 2 with different Lithium doped forms was prepared for the first time. • Ti/Li-6-400 showed the higher activity in transesterification of DMC with BPA. • The activity of surface Ti-O-Li was higher than that of internal Ti-O-Li. • Catalytic activity was related to the alkalinity of catalysts. Lithium doped TiO 2 were prepared by simple impregnation, which was used as heterogeneous catalysts for the transesterification of DMC with BPA. The characterized results of FTIR, XRD, XPS, SEM, TEM and temperature programmed desorption of CO 2 (CO 2 -TPD) showed that the structure and performance of the catalysts were obviously influenced by the doping amount of Li+ and calcining temperature. The optimum catalytic activity was obtained when the molar ratio of Ti/Li reached 6 and the calcination temperature came up to 400 ℃, which was due to Li+ reaction with TiO 2 to form surface Ti-O-Li at 400 ℃ (Ti/Li-6-400). When the transesterification of DMC with BPA was carried out at 160–180 ℃ over Ti/Li-6-400, BPA conversion reached 46.67%, and the yields of one-methylcarbonate-ended-BPA (MmC(1)) and two-methylcarbonate-ended-BPA (DmC(1)) achieved 36.36% and 5.97%, respectively, and only 9.3% methylation selectivity was detected. In addition, the possible transesterification mechanism was provided. [ABSTRACT FROM AUTHOR]