MnO2 cathode materials are widely studied in alkaline and neutral aqueous electrolytes. In these mediums, the MnO2 cathode shows suboptimal performance limited by dissolution and electrochemically inactive compound formation, leading to capacity fading. This study explores the enhancement of MnO2 cathode performance through Bi3 + ion doping (0, 1, 2.5, 5, and 10 mol%) in a highly acidic electrolyte (pH < 2). By incorporating up to 10 mol% Bi ions into the MnO2 structure, we significantly improved specific capacity and capacity retention stability. Energy-dispersive X-ray spectroscopy (EDX) analysis revealed a uniform dispersion of Bi3+ ions throughout the MnO2 cathode after electrochemical cycling, contributing to performance enhancements. X-ray photoelectron spectroscopy (XPS) results indicated that Bi3+ ion concentration from 1 to 10 mol% stabilises Mn3+ within the MnO2 lattice. Also, Bi3+ ion doping promotes the formation of a 2 × 2 tunnel structured α-MnO2 phase. Electrochemical impedance spectroscopy results demonstrated a reduction in double-layer and overall bulk capacitance. These findings suggest that Bi3+ ion doping effectively enhances MnO2 electrochemical performance and could enhance its use in aqueous metal-ion batteries.