AbstractStructural degradation in manganese oxides leads to unstable electrocatalytic activity during long-term cycles. Herein, we overcome this obstacle by using proton exchange on well-defined layered Li₂MnO₃ with an O3-type structure to construct protonated Li_2-xH_xMnO_3-n with a P3-type structure. The protonated catalyst exhibits high oxygen reduction reaction activity and excellent stability compared to previously reported cost-effective Mn-based oxides. Configuration interaction and density functional theory calculations indicate that Li_2-xH_xMnO_3-n has fewer unstable O 2p holes with a Mn^3.7+ valence state and a reduced interlayer distance, originating from the replacement of Li by H. The former is responsible for the structural stability, while the latter is responsible for the high transport property favorable for boosting activity. The optimization of both charge states to reduce unstable O 2p holes and crystalline structure to reduce the reaction pathway is an effective strategy for the rational design of electrocatalysts, with a likely extension to a broad variety of layered alkali-containing metal oxides.