Abstract Li + extraction reactions with spinel-type LiM 0.5Mn 1.5O 4 (M=Ti, Fe) in an aqueous phase were examined using chemical and X-ray diffraction (XRD) analysis. Their electronic structures and chemical bonding properties were also studied using a discrete variational (DV)-Xα molecular orbital method with a cluster model of (Li 5M 4Mn 24O 42) 19+. In the process of extraction reaction, the LiM 0.5Mn 1.5O 4 showed a topotactic extraction of Li + in the aqueous phase mainly through an ion exchange mechanism, and the extracted Li + samples indicated a high selectivity and a large capacity for Li + among 3 d transition metal ions. In order to examine the net charge and magnitude of covalent bondings, Mulliken's population analysis was thoroughly conducted. Its results showed that the Mulliken's charge of Li in LiM 0.5Mn 1.5O 4 was approximately 0.75, regardless of the M-species. The bond overlap population (BOP) of MO was approximately the same as that of MnO in these compounds, and the BOP of FeO was smaller than that of the TiO bonds because the FeO anti-bonding interaction was greater than that of the TiO.