Manganese sesquioxide (Mn2O3), as an cathode material for aqueous zinc ion batteries (AZIBs), has received extensive attention from researchers due to its excellent energy storage potential. However, its application is constrained by factors such as the volume expansion of the material and the poor reversibility caused by manganese dissolution. In order to overcome these limitations, Mn2O3 nanospheres with a unique three-dimensional hollow porous structure were successfully prepared in this study by the hydrothermal method and heat treatment process. This unique three-dimensional hollow porous structure endowed Mn2O3 with a larger specific surface area and superior ion diffusion channels, resulting in excellent zinc storage properties. The Mn-450-2h electrode materials showed a high discharge specific capacity up to 636 mAh/g at a current density of 0.1 A/g and remain at 330 mAh/g after 50 charge/discharge cycles. Meanwhile, the discharge specific capacity of the Mn-450-2h electrode material can be stabilized at 100 mAh/g after 500 cycles at a current density of 0.5 A/g. In addition, a detailed analysis of the electrochemical zinc storage mechanism revealed the relationship between the physicochemical properties and electrochemical performance of the obtained materials, which provides a new perspective and direction for the construction of advanced manganese-based oxide electrode materials.