ABSTRACT Rational design of non‐noble electrocatalysts with high performance for oxygen evolution reaction (OER) still remains a challenge. In this study, a ZIF‐derived electrocatalyst (Co@Fe‐P) with a core‐shell structure is designed by using Co‐compounds as the core and decorated Fe‐compounds as the shell. The inner Co‐core and outer Fe‐shell are connected through Co─O─Fe and Fe─O─P linkage. The Co@Fe‐P electrocatalyst exhibits an enhanced performance for OER with a low overpotential (280 mV), low Tafel slope (41.9 mV dec −1 ) at 10 mA cm −2 , and a 60‐h durability. The electron transfer from the CoOOH‐core to the FeOOH‐shell is greatly facilitated, which improves the OER activity of Co@Fe‐P kinetically. Theoretical calculations indicate that the interaction of Co─O─Fe and Fe─O─P in Co@Fe‐P reduces the overlap between the O 2p and Fe 3d orbitals, which greatly facilitates the transformation from *OH to *O during the OER process via the adsorbate evolution mechanism (AEM) pathway. This finding provides insight for the design of efficient electrocatalysts for OER.