The construction of efficient, durable, and non‐noble metal electrocatalysts for oxygen evolution reaction (OER) is of great value but challenging. Herein, a facile method is developed to synthesize a series of trimetallic (W/Co/Fe) metal–organic frameworks (MOFs)‐derived carbon nanoflakes (CNF) with various Fe content, and an Fe‐dependent volcano‐type plot can be drawn out for WCoFex ‐CNF. The optimized WCoFe0.3‐CNF (when the feed ratio of Fe/Co is 0.3) demonstrates superior electrocatalytic performance with a low overpotential of only 254 mV@10 mA cm−2 and excellent durability of 100 h. Further researches show that appropriate amount of iron doping can regulate the electronic structure, resulting in a favorable synergistic environment. This method may stimulate the exploration of electrocatalysts by utilizing MOFs as precursors while realizing electronic modulation by multimetal doping. Facile synthesis of W/Co/Fe trimetallic carbon nanoflake electrocatalysts which are derived from metal–organic frameworks (MOFs) is reported, and an Fe‐dependent volcano‐type relationship is discovered. Furthermore, the doping content of Fe can accurately modulate the electronic structure of the catalysts. The results highlight the great potential of utilizing multimetallic MOFs as promising templates while realizing electronic structure modulation.