Developing cost-effective and high-efficiency catalysts for electrocatalytic oxygen evolution reaction (OER) is crucial for energy conversions. Herein, a series of bimetallic NiFe metal–organic frameworks (NiFe-BDC) were prepared by a simple solvothermal method for alkaline OER. The synergistic effect between Ni and Fe as well as the large specific surface area lead to a high exposure of Ni active sites during the OER. The optimized NiFe-BDC-0.5 exhibits superior OER performances with a small overpotential of 256 mV at a current density of 10 mA cm−2and a low Tafel slope of 45.4 mV dec−1, which outperforms commercial RuO2and most of the reported MOF-based catalysts reported in the literature. This work provides a new insight into the design of bimetallic MOFs in the applications of electrolysis.