The introduction of NCIL simultaneously achieves a rapid Zn2+ desolvation, homogeneous Zn2+ spatial distribution and the construction of ion-screening interface, thus contributing to a kinetically enhanced and dendrites-free galvanization process. Display omitted Suppression of uncontrollable dendrite growth and water-induced side reactions of Zn metal anodes is crucial for achieving long-lasting cycling stability and facilitating the practical implementations of aqueous Zn-metal batteries. To address these challenges, we report in this study a functional nitro-cellulose interfacial layer (NCIL) on the surface of Zn anodes enlightened by a nitro-coordination chemistry strategy. The NCIL exhibits strong zincophilicity and superior coordination capability with Zn2+ due to the highly electronegative and highly nucleophilic nature of the nitro functional group. This characteristic facilitates a rapid Zn-ion desolvation process and homogeneous Zn plating, effectively preventing H2 evolution and dendrite formation. Additionally, the negatively charged surface of NCIL acts as a shield, repelling SO42− anions and inhibiting corrosive reactions on the Zn surface. Remarkably, reversible and stable Zn plating/stripping is achieved for over 5100 h at a current density of 1 mA cm−2, which is nearly 30 times longer than that of bare Zn anodes. Furthermore, the Zn//V2O5 full cells with the functional interface layer deliver a high-capacity retention of 80.3% for over 10,000 cycles at 5 A g−1. This research offers valuable insights for the rational development of advanced protective interface layers in order to achieve ultra-long-life Zn metal batteries.