CuCoO2 has been used in various catalytic fields because of its unique structure, but its oxygen evolution reaction (OER) performance still needs to be further improved. The current study did not delve into the effect of reaction intermediates on the OER performance of CuCoO2. Therefore, in this study, metal V was introduced to regulate the electronic structure of CuCoO2 and optimize the combination of catalyst and OER intermediates, thus promoting the improvement of OER performance of CuCoO2. In this study, V doped CuCoO2 nanocrystals were successfully synthesized through solvothermal method. The metal V influences the OER performance of CuCoO2 by modulating the crystal structure of CuCoO2. The electronegativity of V is lower than that of Cu, so V can be used to optimize the binding affinity of CuCoO2 with OH- by adjusting dz2 orbitals (O-Co). The electrochemical test results show that 1.5 at% V doped CuCoO2 (CVCO-1.5) yields excellent catalytic performance (η10 = 353 mV, Tafel slope = 69 mV dec−1). The main reason is that V promotes the formation of oxygen vacancies (VO) in CuCoO2 and optimizes the adsorption of reaction intermediates by CuCoO2, thus reducing energy barriers of the reaction. In this work, based on the difference of electronegativity between metals, the binding affinity of the catalysts for OH- is optimized by simple solvothermal method, which can be used as a reference for other delafossite oxide materials and even metal oxide materials.