A unique double-exchange strategy is adopted to access active high-valent transition metal sites during neutral oxygen evolution reaction (OER). This double-exchange is realized through electronic interaction between transition metal ions and foreign dopants in a transition metal oxide. Based on systematical evaluation on dopants with varied d-electron numbers, we demonstrate that the d electron-poor dopant exhibits more significant double-exchange interaction with the transition metal ions, and therefore obtains more active high-valence metal sites, and thus achieves better neutral OER performance.