The integration of Fe dopant and interfacial FeOOH into Ni‐MOFs Fe‐doped‐(Ni‐MOFs)/FeOOH to construct Fe−O−Ni−O−Fe bonding is demonstrated and the origin of remarkable electrocatalytic performance of Ni‐MOFs is elucidated. X‐ray absorption/photoelectron spectroscopy and theoretical calculation results indicate that Fe‐O−Ni−O−Fe bonding can facilitate the distorted coordinated structure of the Ni site with a short nickel–oxygen bond and low coordination number, and can promote the redistribution of Ni/Fe charge density to efficiently regulate the adsorption behavior of key intermediates with a near‐optimal d‐band center. Here the Fe‐doped‐(Ni‐MOFs)/FeOOH with interfacial Fe−O−Ni−O−Fe bonding shows superior catalytic performance for OER with a low overpotential of 210 mV at 15 mA cm−2 and excellent stability with ≈3 % attenuation after a 120 h cycle test. This study provides a novel strategy to design high‐performance Ni/Fe‐based electrocatalysts for OER in alkaline media. Iron doping and FeOOH decorating leads to interfacial Fe−O−Ni−O−Fe bonding in Fe‐doped‐(Ni‐MOF)/FeOOH. This interfacial bonding can regulate the active Ni site to give the appropriate adsorption behavior of intermediates for the oxygen evolution reaction (OER). As a result, Fe‐doped‐(Ni‐MOF)/FeOOH shows outstanding catalytic performance with low overpotential, small Tafel slope, and high durability.