Development of efficient electrocatalysts for water splitting can be a significant step toward green hydrogen generation. In this work, a remarkable enhancement of electrocatalytic properties is achieved through the incorporation of oxygen-vacancies in a perovskite oxide, while maintaining the same structural framework. The oxygen-deficient material La2MnCoO6-δ (LaMn0.5Co0.5O3-δ) is isostructural to the parent stoichiometric material, but shows drastically enhanced electrocatalytic properties for both half-reactions of water-splitting, namely hydrogen-evolution and oxygen-evolution reactions, due to the oxygen-vacancies.