Electrochemical behavior of spinel-type Li[Li x Mn2−x ]O4 samples is examined in sodium containing non-aqueous electrolyte solution. Li ions in stoichiometric LiMn2O4 sample are electrochemically extracted in sodium containing electrolyte solution, forming Li x Mn2O4 (x =0.1) by first oxidation process. Sodium ions are inserted into the lithium extracted spinel phase, which results in the phase transition. From structural analysis by X-ray diffraction and phase transition behavior in the sodium cells, it is found that an original spinel phase in part converts into a layered phase, Na y MnO2. Thus prepared Na y MnO2 can deliver approximately 190–200mAhg−1 of reversible capacity with relatively good capacity retention as positive electrode materials for rechargeable sodium batteries. Nonstoichiometric Li-rich manganese spinel, Li[Li0.2Mn1.8]O4, also accommodates the sodium ions, similarly to the stoichiometric phase. However, phase transition to the layered phase is not observed. Instead, the sodium insertion into Li[Li0.2Mn1.8]O4 induces strain in the crystal lattice.