With exceptional capacity during high-voltage cycling, P3-type Na-deficient layered oxide cathodes have captured substantial attention. Nevertheless, they are plagued by severe capacity degradation over cycling. In this study, tuning and optimizing the phase composition in layered oxides through Li incorporation are proposed to enhance the high-voltage stability. The structural dependence of layered Na2/3LixNi0.25Mn0.75O2+δ oxides on the lithium content (0.0 ≤ x ≤ 1.0) offered during synthesis is investigated systematically on an atomic scale. Surprisingly, increasing the Li content triggers the formation of mixed P2/O3-type or P3/P2/O3-type layered phases. As the voltage window is 1.5–4.5 V, P3-type Na2/3Ni0.25Mn0.75O2 (NL0.0NMO, R