Aqueous Zn batteries are emerging as promising energy storage devices. However, severe dendrite growth and side reactions of Zn anodes restrict their further development. Herein, we develop a nucleophilic interfacial layer (NIL) on Zn to achieve a highly stable Zn anode for rechargeable Zn batteries. The NIL in a composition of zinc acetate acetamide is homogeneous, compact, and Zn2+-conductive, rendering dendrite-free Zn deposition, which is observed by in situ optical microscopy. Benefiting from the advantages of NIL, the Zn||Zn symmetric cells show a low overpotential of 0.12 V at a high current density of 40 mA/cm2, enhanced Coulombic efficiency up to 99.9%, and extended lifespan over 2600 cycles. The Zn||Ti asymmetric cells exhibit a high areal capacity of 5 mAh/cm2. Moreover, the NIL functionalized Zn anode enables stable cycling of both anode-free Zn||Cl2 cells and zinc-ion capacitors, providing opportunities for the development of high-performance energy storage devices.