The production of ecologically compatible fuels by electrochemical water splitting is highly desirable for modern industry. The Zhang-Rice singlet is well known for the superconductivity of high-temperature superconductors cuprate, but is rarely known for an electrochemical catalyst. Herein, we observe two steps of surface reconstruction from initial catalytic inactive Cu1+ in hydrogen treated Cu2O to Cu2+ state and further to catalytic active Zhang-Rice singlet state during the oxygen evolution reaction for water splitting. The hydrogen treated Cu2O catalyst exhibits a superior catalytic activity and stability for water splitting and is an efficient rival of other 3d-transition-metal catalysts. Multiple operando spectroscopies indicate that Zhang-Rice singlet is real active species, since it appears only under oxygen evolution reaction condition. This work provides an insight in developing an electrochemical catalyst from catalytically inactive materials and improves understanding of the mechanism of a Cu-based catalyst for water oxidation.