Design and synthesis efficient non-noble metal bifunctional electrocatalyst for hydrogen and oxygen evolution reactions toward overall water splitting to solve the energy crisis and environmental problems. Herein, we propose a novel post-modification synthesis strategy to prepare the hybrid nanostructure composed of Co2P and MoP nanoparticles (NPs) embedded in N-doped carbon nanosphere (denoted as MoP/Co2P @NCNS-600). Through engineering the anion chemistry of cobaltosic oxide nanoparticles to adjust the composition, morphology and crystallographic orientation of Mo-MOF, then the pyrolysis-phosphidation process, the as-synthesized MoP/Co2P @NCNS-600 catalyst perform excellent electrocatalytic performance (overpotentials (η10) of 270 mV at 10 mA cm-2 for OER and overpotentials (η10) of 62 mV at 10 mA cm-2 for HER), benefiting from the well-designed structure and the synergistic effects between highly active Co2P and MoP. Furthermore, the MoP/Co2P @NCNS-600 serves as both anode and cathode for an overall water-splitting cell, presents a low potential to achieve the current density of 10 mA cm-2.