The development of high efficiency and stable electrocatalysts for the electrochemical water oxidation reaction (WOR) is a grand bottleneck in chemical energy storage and conversion. This article describes a simple co-precipitation route to deposit hierarchical NiCo2S4@Ni3V2O8 core/shell hybrid on conductive nickel foam electrode by a simple two-step process. When it is firstly used as the 3D substrates electrode, the NiCo2S4@Ni3V2O8 material makes use of both components and provides excellent water oxidation activity, 35 mA cm(-2) was achieved at a overpotential of 290 mV, which is better than the benchmark of IrO2 electrodes (320 mV of overpotential at 35 mA cm(-2)) and 13 mA cm(-2) at 1.47 V with excellent durability. The enhanced water oxidation performance of the NiCo2S4@Ni3V2O8 materials is mainly benefiting from its particular core/shell structure, which exhibits big surface areas, and fast electron and ion transfer. Ni3V2O8 shell protects NiCo2S4 core from oxidation in the in alkaline electrolytes and improves stability of NiCo2S4@Ni3V2O8. This indicates that most metal vanadates oxides-based electrodes are promising as an efficient electrocatalyst and shows the advantages of the interfacial effect, which provide a new idea toward high-performance flexible water oxidation fabrication of robust and cheap catalyst sample. (C) 2018 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.