Highly active and noble-metal-free electrocatalysts are inexpensive and can enhance the oxygen evolution reaction (OER) productivity of water decomposition reaction. Consequently, the invention of such catalysts is a significant task while facing difficult challenges. Herein, we synthesized different amounts of Fe-doped Co3V2O8 (Co3(1-x)Fe3xV2O8 (0 <= x <= 0.9)) electrocatalysts, in which the 3d electronic structure of Co could be adjusted by changing the content of Fe, as evidenced by the XPS data. As the x-value increased from 0, 0.25, 0.4, to 0.5, the reactivity of the OER continued to increase, while the further increase of the x-value led to its decrease. Among them, Co1.5Fe1.5V2O8 exhibited the best OER characteristics. At 10 mA cm(-2), its overpotential was 290 mV, and its Tafel slope was 32.8 mV dec(-1). The favorable electronic structure of Co adjusted by Fe-doping and the synergy between Co and Fe could endow it with excellent electrochemical properties. This work demonstrated the potential of Co1.5Fe1.5V2O8 as a noble-metal-free OER electrocatalyst with high activity and stability, providing a possible way to construct efficient OER electrocatalysts using doping strategy.