<p>N-type organic cathodes, which are representative high-capacity organic materials, still exhibit low output voltage when paired with zinc anode in aqueous batteries (typically below 0.8 V vs. Zn²⁺/Zn), thereby limiting their energy densities. In this work, we demonstrate that the strong electron-withdrawing cyano groups in 7,7,8,8-tetracyanoquinodimethane (TCNQ) enable a high output voltage (1.15 V vs. Zn²⁺/Zn). However, challenges such as sluggish redox kinetics and rapid capacity decay arise during Zn²⁺ ion storage. The incorporation of Na⁺ ions and I⁻/I₃⁻ redox mediator in the conventional ZnSO₄ aqueous electrolyte is proposed to address these issues. Comprehensive characterizations reveal that Na⁺ ions preferentially intercalated into TCNQ over Zn²⁺ ions, resulting in a more favorable interlayer spacing adjustment due to their low charge density. Additionally, the iodine redox couple synergistically interacts with the TCNQ redox process, constructing a “cascade” mechanism that chemically oxidizes NaTCNQ, ensuring its complete conversion back to TCNQ. Benefiting from the synergy of Na⁺ and I⁻ ions, the TCNQ cathode demonstrates significant improvement in reversibility, rate capability, and excellent cycle performance of 2000 cycles with a decay rate of 0.0035% per cycle. This work provides a new strategy for optimizing high-performance organic cathodes for aqueous batteries.</p>