<p>Layered NH₄V₄O₁₀ (NVO) cathodes for aqueous zinc-ion batteries face a fundamental trade-off: while NH<Stack> ₄ ⁺ </Stack> pillars stabilize the interlayer structure, their excessive presence limits Zn²⁺ diffusion through space occupation and electrostatic repulsion. Here, we resolve this dilemma through a thermochemical NH⁺ extraction strategy that precisely optimizes interlayer chemistry. Partial NH⁺ removal at 300 °C (NVO-300) simultaneously expands interlayer spacing and maintains structural integrity, enabling excellent electrochemical performance with a capacity of 569.63 mAh g⁻¹ at 0.1 A g⁻¹ and 74.86% retention after 2000 cycles at 5.0 A g⁻¹. Multimodal characterization reveals a triple synergistic mechanism involving reduced Zn²⁺/<Stack> ₄ ⁺ </Stack> repulsion, reversible NH<Stack> ₄ ⁺ </Stack> redox, and cooperative Zn²⁺/H⁺ co-intercalation with V⁵⁺/V⁴⁺/V³⁺ multi-electron reactions. The tailored interlayer environment achieves capacitive-dominated kinetics and fast Zn²⁺ diffusion, while residual NH<Stack> ₄ ⁺ </Stack> prevents structural collapse during cycling. This work establishes thermal extraction as a universal approach for designing high-capacity layered electrodes through precision pillar ion engineering.</p>