Abstract: In industrial zinc electrowinning processes, Pb–Ag alloys (typically containing 0.5%～1.0% Ag (mass fraction)) have been widely adopted as inert anodes due to their mechanical durability and cost-effectiveness. However, these anodes exhibit intrinsic limitations in strongly acidic sulfate electrolytes. The low catalytic activity of Pb–Ag alloys toward the oxygen evolution reaction (OER) leads to elevated anode potential and increased energy consumption during zinc production. This high overpotential not only raises power costs but also accelerates the electrochemical corrosion of the Pb–Ag anode. Specifically, lead on the surface undergoes oxidation, resulting in Pb dissolution into the electrolyte. These dissolved lead ions subsequently co-deposit on the cathode, contaminating the zinc product and reducing its purity. Furthermore, the uneven OER activity induces localized current density hotspots, exacerbating structural degradation and shortening anode service life. To address these issues, pre-coating Pb–Ag anodes with MnO₂ has emerged as a promising solution. MnO₂ coatings effectively enhance the corrosion resistance of Pb–Ag anodes and inhibit surface lead oxidation and dissolution. At the same time, the MnO₂ film serves as an excellent catalytic layer, significantly improving the oxygen evolution performance of the electrode. However, the MnO₂ film prepared via traditional coating processes often suffer from a loose structure, poor adhesion, and limited protective effects on the Pb–Ag substrate. In the electrodeposition process, additives play a crucial role in optimizing deposit quality, adhesion, and performance while ensuring efficient and consistent electroplating results. Inspired by this, the incorporation of additives is anticipated to improve MnO₂ film quality on Pb–Ag anodes. In this study, cetyltrimethyl ammonium bromide (CTAB) was used as an additive to induce the formation of MnO₂ films with enhanced corrosion resistance and OER activity by modulating the electrocrystallization process on the Pb-Ag surface. The results demonstrate that introducing appropriate amounts of CTAB into the zinc electrodeposition system accelerates the oxidation of Mn²⁺ to Mn³⁺ intermediates, promotes uniform electrocrystallization of MnO₂ on the substrate, and significantly enhances both catalytic activity and corrosion resistance of the electrode. Comparative tests between CTAB-modified anodes (PAM-C) and conventionally coated MnO₂ anodes (IPAM) revealed substantial performance improvements. During long-term simulated zinc electrowinning, the CTAB-assisted Pb-Ag/MnO₂ anode prepared with 1 g·L⁻¹ (PAM-C₁) showed superior OER performance and corrosion resistance compared to IPAM. At 500 A·m⁻², the oxygen evolution potential of PAM-C₁ (2.09 V (vs RHE)) was 50 mV lower than that of IPAM (2.14 V (vs RHE)), while maintaining stable performance. After 15 days of electrolysis, the lead concentration in the PAM-C₁-based system decreased from 0.70 mg·L⁻¹ to 0.61 mg·L⁻¹ compared to the IPAM system. The enhanced performance of the PAM-C₁ anode could contribute to more efficient and environmentally friendly zinc production. This work presents a promising approach to reducing energy consumption and improving product quality through additive-regulated MnO₂ coating of Pb–Ag anodes, offering valuable insights for the sustainable development of the zinc electrowinning industry.