To achieve high efficiency of water electrolysis to produce hydrogen (H2), developing non-noble metal-based catalysts with consid-erable performance have been considered as a crucial strategy, which is correlated with both the interphase properties and multi-metal synergistic effects. Herein, as a proof of concept, a delicate NiCo(OH)x-CoyW catalyst with a bush-like heterostructure was realized via gas-template-assisted electrodeposition, followed by an electrochemical etching-growth process, which ensured a high active area and fast gas release kinetics for a superior hydrogen evolution reaction, with an overpotential of 21 and 139 mV at 10 and 500 mA cm-2, respectively. Physical and electrochemical analyses demonstrated that the synergistic effect of the NiCo(OH)x/CoyW heteroge-neous interface resulted in favorable electron redistribution and faster electron transfer efficiency. The amorphous NiCo(OH)x strengthened the water dissociation step, and metal phase of CoW provided sufficient sites for moderate H immediate adsorption/H2 desorption. In addition, NiCo(OH)x-CoyW exhibited desirable urea oxidation reaction activity for matching H2 generation with a low voltage of 1.51 V at 50 mA cm-2. More importantly, the synthesis and testing of the NiCo(OH)x-CoyW catalyst in this study were all solar-powered, sug-gesting a promising environmentally friendly process for practical applications.