Sn metal is a preferable choice as anode material for aqueous acidic batteries due to its acid‐tolerance, non‐toxicity, and ease of recycling. However, the large size and irregular deposition morphology of polyhedral Sn particles are bad for constructing stable and high‐capacity Sn metal anode because of severe hydrogen evolution and metal shedding. To tackle this critical issue, 4‐tert‐octylphenol pentaethoxylate (POPE) is used as an electrolyte additive to generate a thin‐film Sn anode with reversible stripping/plating behavior. POPE can not only induce homogeneous surface chemistry by adsorbing on the Sn surface via coordination bonds but also inhibit hydrogen evolution by modulating the solvation shell of Sn2+. The Sn film anode delivers improved electrochemical stability over 480 h with satisfactory rate performance and low polarization. Moreover, the as‐assembled PbO2//Sn battery can also provide outstanding durability at 10 mAh cm−2. This work offers new inspiration for developing a reversible Sn metal film anode.