The electrochemical performance of heat treated manganese dioxide in lithium batteries is for the first time directly related to the numerous physical properties which characterize this battery material. The effect of discharge rate on these relationships is also investigated. Three of these properties are considered, revealing that at low discharge rates heat treated manganese dioxide is optimized by a pyrolusite fraction of ∼0.65, high Mn(IV), and low surface area; while at high discharge rates slightly higher pyrolusite content (∼0.73), high Mn(IV), and surface area around 44 m2 g−1 are most beneficial. The relationships described here will assist in directing the synthesis and preparative treatment of manganese dioxides for higher performing lithium batteries.