Dual metal doping and optimization are considered as vital approaches for enhancing the electrocatalytic features toward oxygen evolution reaction. Herein, a sequence of Fe and V dual metal‐doped mesoporous cobalt oxide (FeV/meso‐Co) electrocatalysts was successfully synthesized through citric acid‐assisted evaporation‐induced self‐assembly (EISA) method. The textural, morphological, crystallinity, and electrochemical activities of Fe/V‐promoted meso‐Co (124 m2/g) are found strongly associated with dual (Fe and V) metal concentration. Benefiting from the combined effect of FeV‐doping, the FeV/meso‐Co exhibited an extremely lower overpotential of 280 mV to reach 10 mA/cm2 for oxygen evolution reaction (OER) in 1M KOH electrolyte, which was the considerably lowest value among the earlier catalysts, and the FeV/meso‐Co showed similar features as IrO2 electrodes. Furthermore, FeV/meso‐Co electrodes display highly durable (>30 hours) electrocatalytic performance for OER. This inexpensive approach of producing transition dual metal‐doped mesoporous materials offers excellent promise for fabricating efficient catalysts and other electrochemical energy‐conversion devices.