Abstract: N-doped MoP-based core-shell nanorods (N-MoP/NC-8) were synthesized by in-situ phosphorization of molybdenum trioxide-ethylenediamine organic-inorganic hybrid material (MoO₃/EDA) via a gas-solid reaction; their electrocatalytic performance in hydrogen evolution was investigated. The results indicate that N-MoP/NC-8 is composed of N-doped molybdenum phosphide (MoP) coated by N-doped carbon layer. The introduced electronegative atom can regulate the electronic structure of the active phase, whilst the combination of carbon layer and MoP can inhibit the internal agglomeration of MoP, resulting in large pore volume and surface area. Owing to such a dual effect, the N-MoP/NC-8 catalyst shows excellent performance in electrocatalytic hydrogen evolution and great charge transfer ability; the overpotential is 92 mV at 10 mA/cm² current density in 0.5 mol/L H₂SO₄ solution, with a Tafel slope of 68 mV/dec and a durability of above 20 h.