The design and synthesis of high-activity earth-abundant material-based electrocatalysts for hydrogen evolution reaction (HER) are of great significance. Here we develop a novel method to prepare a MoP nanoparticle supported on N,P-codoped reduced graphene oxides (MoP/N,P-rGO) by pyrolysis of the self-assembled precursor. Benefiting from the selected components of the assembly, P and N atoms are mixed at the molecular level, which leads to MoP nanoparticles uniformly attaching to the graphene substrate and a certain amount of N and P atoms codoping to graphene. The obtained MoP/N,P-rGO exhibits a good HER performance that only needs an overpotential of 115 mV to achieve a HER current density of 10 mA cm(-2). The enhanced HER performance is due to the well-dispersed MoP nanoparticles and the synergistic effect from the doped graphene substrate. It shows that the selected functional components integrated by the self-assembly process are appropriate precursors for the synthesis of high-quality HER electrocatalysts.