Aqueous zinc-manganese batteries face the critical issue of irreversible dissolution/deposition of manganese dioxide (MnO₂) stemmed from the disproportionation of Mn³⁺. Herein, the fluorine-doped manganese acetylacetonate-derived carbon (F-MDC) was designed as the cathode substrate to realize reversible dissolution/deposition of MnO₂. An *OH-mediated deposition pathway of MnO₂ was elucidated as follows: *OH → *MnOH → *Mn(OH)₂ → *MnOOH → *MnO₂. Attributed to the high electronegativity of fluorine on F-MDC, such pathway was promoted by accelerating the MnOOH dehydrogenation and strengthening the binding between Mn²⁺ and *OH, which could effectively avoid the disproportionation of Mn³⁺ and the formation of “dead MnO₂”. The Zn-Mn battery based on F-MDC delivered a capacity retention rate of 91.7% after 4000 cycles at 3 A g⁻¹ and still retained the specific capacity of 87.5 mAh g⁻¹ even at a high current density of 10 A g⁻¹. In addition, the assembled pouch cell also displayed standout rate capability, cycling stability and power supply performance.