The primary capacity of heat treated manganese dioxide in Li/MnO2 batteries is directly related to the numerous physical properties which characterize this material. A statistical model is employed to isolate the influence of material structure, composition and morphology on the electrochemical performance at the discharge rates 2, 5, 10 and 20mAg−1. Among the most influential parameters are the pyrolusite content, Mn(IV) percentage, cation vacancy fraction and surface area. Some of the materials investigated show higher specific capacities than literature materials, with further improvement to the performance of these materials anticipated through the intelligent selection of heat treated manganese dioxide which exhibit the ideal properties outlined in this study.