Aqueous zinc-ion batteries (AZIBs) have shown great potential as energy storage devices owing to their high energy density, low cost, and low toxicity. Typically, high performance AZIBs incorporate manganese-based cathode materials. Despite their advantages, these cathodes are limited by significant capacity fading and poor rate performance due to the dissolution and disproportionation of manganese. Herein, hierarchical spheroidal MnO@C structures were synthesized from Mn-based metal-organic frameworks, which benefit from a protective carbon layer to prevent manganese dissolution. The spheroidal MnO@C structures were incorporated onto a heterogeneous interface to act as a cathode material for AZIBs, which exhibited excellent cycling stability (160 mAh g-1 after 1000 cycles at 3.0 A g-1), good rate capability (165.9 mAh g-1 at 3.0 A g-1), and appreciable specific capacity (412.4 mAh g-1 at 0.1 A g-1) for AZIBs. Moreover, the Zn2+ storage mechanism in MnO@C was comprehensively investigated using ex-situ XRD and XPS studies. These results demonstrate that hierarchical spheroidal MnO@C is a potential cathode material for high-performing AZIBs.