Air-stability is one of the most important considerations for the practical application of electrode materials in energy-harvesting/storage devices, ranging from solar cells to rechargeable batteries. The promising P2-layered sodium transition metal oxides (P2-Na_xTmO₂) often suffer from structural/chemical transformations when contacted with moist air. However, these elaborate transitions and the evaluation rules towards air-stable P2-Na_xTmO₂ have not yet been clearly elucidated. Herein, taking P2-Na_0.67MnO₂ and P2-Na_0.67Ni_0.33Mn_0.67O₂ as key examples, we unveil the comprehensive structural/chemical degradation mechanisms of P2-Na_xTmO₂ in different ambient atmospheres by using various microscopic/spectroscopic characterizations and first-principle calculations. The extent of bulk structural/chemical transformation of P2-Na_xTmO₂ is determined by the amount of extracted Na⁺, which is mainly compensated by Na⁺/H⁺ exchange. By expanding our study to a series of Mn-based oxides, we reveal that the air-stability of P2-Na_xTmO₂ is highly related to their oxidation features in the first charge process and further propose a practical evaluating rule associated with redox couples for air-stable Na_xTmO₂ cathodes.