The oxygen reduction reaction (ORR) has been demonstrated as a critical technology for both energy conversion technologies and hydrogen peroxide intermediate production. Herein, an in situ oxygen evolution reaction (OER) surface evolution strategy is applied for changing the surface structure of MnCo2O4 oxide with tetrahedral and octahedral cations vacancies to realize reaction pathway switching from 2e− ORR and 4e− ORR. Interestingly, the as‐synthesized MnCo2O4‐pristine (MnCo2O4‐P) with the highest surficial Mn/Co octahedron occupation favors two electrons reaction routes exhibiting high H2O2 selectivity (≈80% and reaches nearly 100% at 0.75 V vs RHE); after surface atoms reconstruction, MnCo2O4‐activation (MnCo2O4‐A) with the largest Mn/Co tetrahedron occupation present excellent ORR performance through the four‐electron pathway with an ultrahigh onset potential and half‐wave potential of 0.78 and 0.92 V, ideal mass activity (MA), and turnover frequencies (TOF) values. Density functional theory (DFT) calculations reveal the concurrent modulations of both Co and Mn by the surface reconstructions, which improve the electroactivity of MnCo2O4‐A toward the 4e− pathway. This work provides a new perspective to building correlation of OER activation–ORR property, bringing detailed understating for reaction route transformation, and thus guiding the development of certain electrocatalysts with specific purposes.