most valuable fundamental chemicals in various chemical industries, medical industries, and environmental remediation. [2] Interestingly, both these two focuses can be realized by the ORR process via different reaction routes or mechanisms. In detail, ORR with a complex multielectron process can proceed by two pathways, including the four-electron (4e − ) or two-electron 2e − ORR process to generate H 2 O or H 2 O 2 , respectively. [3] In the former pathway, oxygen is directly reduced to the final OHwhich is usually facilitated by platinum (Pt)based noble-metal electrocatalysts or some non-noble materials; while for the latter one, the first formed peroxide intermediateswill either diffuse away from the disk electrode or continues to be reduced to form OH − (H 2 O 2 + 2e − → 2OH − ), which is commonly occurred on the surface of carbonaceous materials or transition-metal oxides. [4] As illustrated, the mechanism for ORR is strongly affected by the surface structure, coordination environment, really exposed active centers, or crystal types of catalysts. [5] Among all the reported catalysts, typical mixed-metal cobalt manganese oxides (Mn x Co 3−x O 4±δ , 0 ≤ x ≤ 3, where δ indicates the oxygen non-stoichiometry) are usually deemed as promising catalysts in the oxygen electrochemical reaction, owing to high element abundance, considerable electro-activity, controllable tetrahedral and octahedral coordination, rich valence states. [6] Currently, various kinds of Mn-Co oxides have been reported for ORR; 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 MnCo 2 O 4 oxide with tetrahedral and octahedral cations vacancies to realize reaction pathway switching from 2e − ORR and 4e − ORR. Interestingly, the as-synthesized MnCo 2 O 4 -pristine (MnCo 2 O 4 -P) with the highest surficial Mn/Co octahedron occupation favors two electrons reaction routes exhibiting high H 2 O 2 selectivity (≈80% and reaches nearly 100% at 0.75 V vs RHE); after surface atoms reconstruction, MnCo 2 O 4 -activation (MnCo 2 O 4 -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 MnCo 2 O 4 -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.