Zn metal, as one of the most promising anode materials for aqueous batteries, suffers from uncontrollable dendrite growth and water-induced parasitic reactions, which drastically compromise its cycle life and Coulombic efficiency (CE). Herein, we propose a nonionic amphipathic additive Tween-20 (denoted as TW20) that bears both zincophilic and hydrophobic units. The zincophilic segment of TW20 preferentially adsorbs on the Zn anode, while the hydrophobic segment is exposed on the electrolyte side, forming an electrolyte-facing hydrophobic layer that shields the anode from active water molecules. Moreover, theoretical calculation and experimental results reveal that the TW20 additive is able to induce the preferential growth of the (002) plane by adsorbing on other facets, enabling a highly reversible and dendrite-free Zn anode. Benefitting from the multi-functional TW20 additive, the long-term stability and reversibility of Zn anodes are substantially improved, reflected by stable cycling for over 2500 h at 1.0 mA cm-2/1.0 mAh cm-2 and 500 h at 5 mA cm-2/5 mAh cm-2 as well as high reversibility with a high average CE of 99.4% at 1.0 mA cm-2/1.0 mAh cm-2. The full cells paired with MnO2 demonstrate a long lifespan for more than 700 cycles at 500 mA g-1. This work is expected to provide a new approach to modulate Zn electrode interface chemistry for highly stable Zn anode in aqueous zinc ion batteries. This article is protected by copyright. All rights reserved.