Diverse structures of Mn oxides in natural and engineered systems occur from the transformation of δ- MnO2, the most common crystalline phase of nucleated Mn oxides, to other structures via redox reactions, adsorption of metals, etc. Recently, together with emerging interests of Zn-based rechargeable battery systems, which use Mn oxides as a cathode, the transformation and recrystallization of Mn oxides have garnered interests. Here, using hydrothermal reaction of Zn-doped δ-MnO2, the formation of todorokite and chalcophanite is observed. When the concentration of doped Zn increases, the formation of chalcophanite is dominant, but occurs slower than that of the lower concentration of doped Zn. This study will provide a new understanding of the effect of Zn on the recrystallization process of Mn oxides during redox cycles in energy storage systems and environmental systems.