Aqueous zinc-ion batteries are highly favored for grid-level energy storage owing to their low cost and high safety, but their practical application is limited by slow ion migration. To address this, a strategy has been developed to create a cation-accelerating electric field on the surface of the cathode to achieve ultrafast Zn2+ diffusion kinetics. By employing electrodeposition to coat MoS2 on the surface of BaV6O16·3H2O nanowires, the directional built-in electric field generated at the heterointerface acts as a cation accelerator, continuously accelerating Zn2+ diffusion into the active material. The optimized Zn2+ diffusion coefficient in CC@BaV6O16·3H2O@MoS2 (7.5×10−8 cm2 s−1) surpasses that of most reported V-based cathodes. Simultaneously, MoS2 serving as a cathodic armor extends the cycling life of the Zn-CC@BaV6O16·3H2O@MoS2 full batteries to over 10,000 cycles. This work provides valuable insights into optimizing ion diffusion kinetics for high-performance energy storage devices.