<p>This study comprehensively investigates the corrosion behavior and underlying mechanisms of zinc and zinc–aluminum alloy coatings under neutral salt spray conditions. A multi-scale analytical approach integrating macroscopic and microscopic morphological characterization, corrosion kinetics analysis, and conventional electrochemical techniques was employed to elucidate the complete corrosion process. The corrosion resistance of both coatings was systematically evaluated, revealing the superior durability of the zinc–aluminum alloy coating, which is attributed to its distinct corrosion-inhibiting mechanisms. Significant differences in phase composition and corrosion product film structure were observed between the two coatings. The zinc coating consists of a single zinc phase, whereas the zinc–aluminum alloy coating contains zinc, aluminum, and Zn–Al intermetallic phases. The predominant corrosion products of the zinc coating are ZnO and Zn₅(OH)₈Cl₂·H₂O, while those formed on the zinc–aluminum alloy coating are primarily Al₂O₃ and ZnAl₂(OH)₈CO₃. In the zinc–aluminum alloy system, the zinc phase preferentially corrodes, providing sacrificial anodic protection, while the formation of a passive aluminum oxide film further enhances corrosion resistance. In addition, the generation of layered double hydroxides (LDHs) contributes to the dynamic self-healing of the corrosion product layer. Compared with conventional zinc coatings, the zinc–aluminum alloy coating exhibits a 2.5- to 3-fold improvement in corrosion resistance.</p>