Since the catalytic activity of present nickel-based synthetic selenide is still to be improved, MoSe2-Ni3Se2 was synthesized on nickel foam (NF) (MoSe2-Ni3Se2/NF) by introducing a molybdenum source. After the molybdenum source was introduced, the surface of the catalyst changed from a single-phase structure to a multi-phase structure. The catalyst surface with enriched active sites and the synergistic effect of MoSe2 and Ni3Se2 together enhance the hydrogen evolution reactions (HER), the oxygen evolution reactions (OER), and electrocatalytic total water splitting activity of the catalyst. The overpotential of the MoSe2-Ni3Se2/NF electrocatalyst is only 259 mV and 395 mV at a current density of 100 mA/cm2 for HER and OER, respectively. MoSe2-Ni3Se2/NF with a two-electrode system attains a current density of 10 mA/cm2 at 1.60 V. In addition, the overpotential of HER and OER of MoSe2-Ni3Se2/NF within 80000 s and the decomposition voltage of electrocatalytic total water decomposition hardly changed, showing an extremely strong stability. The improvement of MoSe2-Ni3Se2/NF catalytic activity is attributed to the establishment of the multi-phase structure and the optimized inoculation of the multi-component and multi-interface.