A hybrid electrocatalyst composed of NiCoP and MoxC has been prepared via the two-step calcination method. Microscopic analysis demonstrates that the heterojunctions formed by the NiCoP and MoxC are disordered and stacked irregularly. The NiCoP/MoxC heterojunctions are produced during the second calcination treatment. The synergistic effects promote water adsorption and dissociation, and H2 desorption. More active sites are provided by the irregular structure, the NiCoP/MoxC-X catalyst are imparted excellent electrocatalytic activity toward hydrogen evolution reaction (HER) activity. To sustain a current density of 10.0 mA/cm2, the overpotentials of NiCoP/MoxC-15 are 79.0 and 116.0 mV while the Tafel slopes are 52.3 and 57.4 mV/dec for the electrocatalyst operated in 1.0 M KOH and 0.50 M H2SO4, respectively. When operating in alkaline medium for 10.0 h at an overpotential of 123.0 mV, the retaining catalytic activity of this material reaches 93.0%.