The hydrothermal-electrochemical synthesis route has been used to prepare a variety of MnO2 compounds with the α, β and γ structure types as well as intimate mixtures of these structure types. The γ-MnO2 compounds can be synthesized with varying amounts of pyrolusite intergrowth, and low occurrence of microtwinning defects. The influence of the synthesis parameters (temperature, pH, applied current density, composition of the synthesis solution) on the type of structure obtained are discussed. The morphology of some of the compounds obtained is presented. A lithium insertion study compares the behavior of α- and γ-MnO2. The α-MnO2 shows a very stable capacity of 145mAh/g at a discharge rate of C/10.