Aqueous zinc-manganese (Zn-Mn) batteries have promising potential in large-scale energy storage applications since they are highly safe, environment-friendly, and low-cost. However, the practicality of Mn-based materials is plagued by their structural collapse and uncertain energy storage mechanism upon cycling. Herein, this work designs an amorphous manganese borate (a-MnBOx) material via disordered coordination to alleviate the above issues and improve the electrochemical performance of Zn-Mn batteries. The unique physicochemical characteristic of a-MnBOx enables the inner a-MnBOx to serve as a robust framework in the initial energy storage process. Additionally, the amorphous manganese dioxide, amorphous ZnxMnO(OH)2, and Zn4SO4(OH)6-4H2O active components form on the surface of a-MnBOx during the charge/discharge process. The detailed in situ/ex situ characterization demonstrates that the heterostructure of the inner a-MnBOx and surface multicomponent phases endows two energy storage modes (Zn2+/H+ intercalation/deintercalation process and reversible conversion mechanism between the ZnxMnO(OH)2 and Zn4SO4(OH)6-4H2O) phases). Therefore, the obtained Zn//a-MnBOx battery exhibits a high specific capacity of360.4 mAh g-1, a high energy density of484.2 Wh kg-1, and impressive cycling stability (97.0% capacity retention after 10 000 cycles). This finding on a-MnBOx with a dual-energy storage mechanism provides new opportunities for developing high-performance aqueous Zn-Mn batteries. [ABSTRACT FROM AUTHOR]