Developing low‐cost, effective and durable oxygen evolution catalysts (OECs) is still a huge challenge due to the uphill reaction in thermodynamics and the involvement of 4 electrons and 4 protons process in kinetics. Herein, a facilely prepared NiCoFe(OH)x/NiOOH/NF electrode affords current densities of 10 and 100 mA cm‐2 at overpotentials of 223 and 254 mV, respectively, and Tafel slope as low as 33.5 mV dec‐1 in 1 M KOH, which is superior to NiCoFe(OH)x/NF electrodes electrodeposited with traditional method. This electrode also displays surprisingly high durability at a current density of 50 mA cm‐2 for over 50 h under the alkaline conditions. Component analysis and electrochemical study reveal that the catalytic activity enhancement of this newly prepared electrode is mainly attributed to the formation of the electrically conductive NiOOH interlayer.