Understanding and controlling the polymorphism of manganese dioxide (MnO 2 ) is of vital importance in many nanoscale applications. Here in situ powder X-ray diffraction (PXRD) in combination with in situ total X-ray scattering are used to reveal the formation mechanism as well as polymorph evolution of MnO 2 under hydrothermal synthesis conditions. A "PXRD invisible" amorphous phase with a local structure resembling α-MnO 2 (denoted α-MnO 2 (A)) is observed at all reaction stages, and it never fully disappears from the reaction solution. The MnO 2 phase evolution involves initial formation of δ-MnO 2 , which transforms to α-MnO 2 , and then subsequently to β-MnO 2 . The phase transformations between different polymorphs do not involve dissolution−recrystallization, but they occur via solid-state mechanisms. However, the amorphous α-MnO 2 (A) phase plays a key role since it is consumed in growing both the αand β-MnO 2 polymorphs. Overall, the polymorphism of the crystalline product can be controlled through reaction time and temperature to form either nanocrystalline and disordered δ-MnO 2 , nanocrystalline α-MnO 2 , or nanocrystalline β-MnO 2 . At the lowest temperature (200 °C) the very early growth of α-MnO 2 appears to be by oriented attachment along (110) crystal planes of primary nanorods, but this is quickly followed by rapid growth along the c-direction supported by consumption of α-MnO 2 (A).