The atomically precise mental nanoclusters have been widely explored in catalysis. However, the easy aggregation of clusters limits their application. The porous structure of metal-organic framework can prevent the aggregation and growth of clusters. In this work, a copper-phosphine complex: Cu2(dppm)2(PF6)2 (Cu2) was synthesized by one-pot method and then reacted with hydrogen sulfide to obtain a tetranuclear copper cluster: Cu4(S)(dppm)4(PF6)2 (Cu4). The two copper clusters were successfully introduced into Zeolitic imidazole frameworks-67 (ZIF-67) to form Cu2-ZIF-67 and Cu4-ZIF-67. It found that after the introduction of Cu cluster, the pore size of ZIF-67 was increased leading to more exposed Co2+ and more unsaturated coordination mental sites, which is beneficial for electrochemical oxygen evolution reaction (OER). The OER ability of pure ZIF-67 was enhanced after the introduction of Cu2 and Cu4 clusters, in which Cu4-ZIF-67 displayed the best electrochemical performance. At 10 mA cm−2, it requires an overpotential of 340 mV. The lower Tafel slope and smaller charge transfer resistance reflect its faster dynamic process. This work provides a new idea for the development of OER electrocatalysts.