Mingquan Liu, Yun Huang, Haotian Hou, Yinze Zuo, Junming Cai, Jie Lei, Xin Feng, Qiao Ni, Wei Yan, Jiujun Zhang, Chuan Wu
ABSTRACT Controlling Zn (100) oriented deposition offers a promising route for highly reversible Zn anodes, yet the intrinsic susceptibility to parasitic reactions and unbalanced interfacial kinetics of this facet pose critical challenges. Herein, inspired by the biological regulation of inflammatory stress, sulfated polysaccharides are proposed as sustainable electrolyte additives. Specifically, dextran sulfate sodium (DSS) enables durable Zn (100) plating/stripping and balanced interfacial kinetics. The high‐density continuously grafted ─SO 3 − bonds in DSS can rebuild Zn 2+ solvation structure and construct a robust interfacial layer to mitigate parasitic reaction and dendrite formation. Preferred absorption of DSS on (100) facet through ─SO 3 − bonds restrict Zn growth along this facet and facilitate Zn 2+ diffusion from adjacent (002)/(101) facets, ultimately exposing Zn (100) texture. Multiple ─SO 3 − bonds enable fast desolvation and ionic transport kinetics, and steric hindrance of DSS ensures moderated Zn 2+ reduction kinetics, synergistically establishing a kinetics‐balanced interface for durable Zn (100) deposition. Consequently, the DSS‐modified electrolyte achieves exceptional cycling stability (10400 h at 1 mA cm −2 ) and high‐rate capability (1500 h at 20 mA cm −2 ) for (100)‐oriented Zn anodes. The broad compatibility with various cathodes underscores the practical promise of this strategy. This work highlights rational molecular design in regulating crystallographic orientation and interfacial kinetics for advanced Zn metal batteries.