The conversion and storage of clean renewable energy can be achieved using water splitting. However, water splitting exhibits sluggish kinetics because of the high overpotentials of the oxygen evolution reaction (OER) and the hydrogen evolution reaction (HER) and should therefore be promoted by OER and/or HER electrocatalysts. As the kinetic barrier of the former reaction exceeds that of the latter, high-performance OER catalysts are highly sought after. Herein, K-doped NiCo2O4 (HK-NCO) was hydrothermally prepared from a Prussian blue analog with a metal-organic framework structure and assessed as an OER catalyst. Extensive K doping increased the number of active oxygen vacancies and changed their intrinsic properties (e.g., binding energy), thus increasing conductivity. As a result, HK-NCO exhibited a Tafel slope of 49.9 mV dec(-1) and a low overpotential of 292 mV at 10 mA cm(-2), outperforming a commercial OER catalyst (Ir) and thus holding great promise as a component of high-performance electrode materials for metal-oxide batteries and supercapacitors.