Zn metal as one of promising anode materials for aqueous batteries but suffers from disreputable dendrite growth, grievous hydrogen evolution and corrosion. Here, a polycation additive, polydiallyl dimethylammonium chloride (PDD), is introduced to achieve long‐term and highly reversible Zn plating/stripping. Specifically, the PDD can simultaneously regulate the electric fields of electrolyte and Zn/electrolyte interface to improve Zn2+ migration behaviors and guide dominant Zn (002) deposition, which is veritably detected by Zeta potential, Kelvin probe force microscopy and scanning electrochemical microscopy. Moreover, PDD also creates a positive charge‐rich protective outer layer and a N‐rich hybrid inner layer, which accelerates the Zn2+ desolvation during plating process and blocks the direct contact between water molecules and Zn anode. Thereby, the reversibility and long‐term stability of Zn anodes are substantially improved, as certified by a higher average coulombic efficiency of 99.7 % for Zn||Cu cells and 22 times longer life for Zn||Zn cells compared with that of PDD‐free electrolyte. [ABSTRACT FROM AUTHOR]