Although Zn metal has been regarded as the most promising anode for aqueous batteries, its practical application is still restricted by side reactions and dendrite growth. Herein, an in-situ solid electrolyte interphase (SEI) film formed on the interface of electrode/electrolyte during the plating/stripping of zinc anodes by introducing trace amounts of multidentate ligand sodium diethyldithiocarbamate (DDTC) additive into 1 M ZnSO₄. The synergistic effect of in-situ solid electrolyte interphase forming and chelate effect endows Zn²⁺ with uniform and rapid interface-diffusion kinetics against dendrite growth and surface side reactions. As a result, the Zn anode in 1 M ZnSO₄ + DDTC electrolytes displays an ultra-high coulombic efficiency of 99.5% and cycling stability (more than 2000 h), especially at high current density (more than 600 cycles at 40 mA cm⁻²). Moreover, the Zn//MnO₂ full cells in the ZnSO₄ + DDTC electrolyte exhibit outstanding cyclic stability (with 98.6% capacity retention after 2000 cycles at 10 C). This electrode/electrolyte interfacial chemistry modulated strategy provides new insight into enhancing zinc anode stability for high-performance aqueous zinc batteries.