Oxygen evolution reaction (OER) from water using transition metal-based catalyst is of significance for the wide spread of future renewable energy materials. Herein, we propose a novel strategy to synthesize cobalt iron oxides (CoFe2O4) with different ordered mesoporous structure by using a facial hard template method. Benefiting from the ordered mesoporous structure, the optimized electrocatalyst achieved a small overpotential of 342 mV to reach 10 mA cm(-2) current density, a low Tafel slope of 57.1 mV dec(-1) in a 1 M KOH aqueous medium, and excellent stability for 15 h, which OER performance is the best after the comparison of lasted reported CoFe2O4-based electrocatalysts. This work not only provides an approach for synthesizing efficient OER catalysts but also highlights a novel tactic to optimize the OER electrocatalysts according to regulate the porous structure.