The discharge characteristics of manganese dioxide (γ-MnO₂ of electrolytic manganese dioxide (EMD) type) as a cathode material in a Zn–MnO₂ battery containing saturated aqueous LiOH electrolyte have been investigated. The X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) data on the discharged material indicate that lithium is intercalated into the host structure of EMD without the destruction of its core structure. The XPS data show that a layer of insoluble material, possibly Li₂CO₃, is deposited on the cathode, creating a barrier to H₂O, thus preventing the formation of Mn hydroxides, but allowing the migration of Li ions into the MnO₂ structure. The cell could be reversibly charged with 83% of voltaic efficiency at 0.5 mA/cm² current density to a 1.9 V cutoff voltage. The percentage utilization of the cathode material during discharge was 56%.