Developing cheaper but efficient electrocatalysts toward hydrogen evolution reaction (HER) are highly desirable for the sustainable energy conversion techniques. The nanostructured CoP has been proved to be one of the most efficient non-noble metal HER catalyst. However, to further improve their performance in hydrogen evolution reaction (HER) is still a challenging task. In the present work, we prepare thenanohybrid CeO2-CoP-C catalyst with high porosity through a co-ionic-exchange with Co and Ce ions using the metal-organic frameworks (MOFs) as template followed with a low-temperature phosphorization route. The high porosity of the catalysts is conductive to the diffusion and mass transfer of the reactants on the catalyst surface. Meanwhile, the doping of rare earth (RE) element modulates the electronic structure of the CoP nanoparticles, and the carbon skeleton left over from the annealed MOF is beneficial to the electronic conduction in the catalyst. Electrochemical tests showed that the ternary CeO2-CoP-C/CC hybrid nanostructure presented overpotential of 71 mV at 10 mV cm(-2) (eta(10)), which is much higher than that of the binary CoP-C/CC catalysts (i.e., 132 mV). In addition, the ternary catalyst also presented a superior long-term durability in an acidic electrolyte. This work opens up a potential strategy for designing more efficient CoP-based catalysts toward electrochemical water splitting. (C) 2018 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.