<p>The efficiency of hydrogen production from water electrolysis as an efficient and clean energy conversion technology is mainly limited by the kinetically retarded oxygen evolution reaction (OER), so the development of highly efficient anode oxygen evolution reaction electrocatalysts is necessary. While metal–organic framework (MOFs) materials are among the materials with the greatest potential to replace traditional noble metal catalysts, they usually cannot be directly used for OER. Therefore, in this paper, novel core–shell structure MIL- 101(Fe)@ZIF- 67 catalysts were prepared by solvothermal and in situ growth method with the assistance of PVP. The electrochemical test results show that the composite MIL- 101(Fe)@ZIF- 67 has excellent oxygen evolution performance. The overpotential of MIL- 101(Fe)@ZIF- 67 at a current density of 10 mA‧cm⁻² was only 330 mV, and the Tafel slope was 48.32 mV‧dec⁻¹, which was significantly better than that of single ZIF- 67(448 mV) and MIL- 101(Fe)(540 mV). The improved performance is mainly due to the large specific surface area and abundant porous structure of MIL- 101 (Fe) and ZIF- 67, which facilitates the transfer of electrons and ions. As well as the synergistic effect between MIL- 101 (Fe) and ZIF- 67, it increases the electrochemically active area and reduces the charge transfer resistance, thus improving the catalytic performance. This research offers new methods and strategies for the preparation of highly efficient electrocatalytic oxygen evolution catalysts.</p>