Mesoporous Ni-CeO2 catalyst was prepared by a polymer (P123)-assisted co-precipitation method and used for reverse water-gas shift reaction. Compared with the catalysts prepared by traditional co-precipitation methods, the mesoporous Ni-CeO2 catalyst shows higher stability for the reverse water-gas shift reaction at 600 degrees C but with no formation of the side product CH4. Moreover the mesoporous Ni-CeO2 catalyst is also highly active for reverse water-gas shift reaction. TPR and XRD results suggest that, in the mesoporous Ni-CeO2 catalyst, Ni2+ ions are incorporated into the CeO2 lattice to form a NixCeyO(2) solid solution, which produces a large number of oxygen vacancies and enhances the reducibility of the surface CeO2. The excellent performance of the mesoporous catalyst is related to the lack of exposed NiO particle on the surface, and the large amount of oxygen vacancies in the uniform mesoporous structure.