Developing a highly effective and durable bifunctional non-noble catalyst is necessary for water electrolysis. In this work, we synthesize the N-doped carbon-coated Ni–MoO2 nanowire heterostructure catalyst anchored on nickel foam for boosting the hydrogen and oxygen evolution reaction (HER and OER). Electrochemical results indicate that it exhibits low overpotentials for HER (50 and 304 mV) and OER (240 and 400 mV) at ±10 and ±2000 mA cm–2. Furthermore, it can keep for 340 h under a multicurrent-process condition (10–1500 mA cm–2) as a cathode and anode without obvious attenuation. The outstanding performance could be ascribed to the heterostructure existing in Ni and MoO2, N-doped-carbon coating structure, and nanowire architecture anchored on nickel foam. This work could provide an industrially promising, cheap, and green method for hydrogen production.