A Zn-based coating with durable hydrophobicity and good corrosion resistance was formed on a mild steel substrate, which involves electroplating Zn from a non-aqueous electrolyte, followed by passivation in an oleic acid (OA) solution. The electrodeposited Zn coatings were porous, which facilitated the formation of a chemical conversion layer of Zn oleate (ZO) during OA passivation. The Zn coating after passivation had a twolayer structure, which included an outer layer of ZO with a thickness of ~26 μm and an inner layer of Zn with a thickness of ~6 μm. The outer layer ZO is a type of metal soap with a smooth surface and durable hydrophobicity, such that water droplets can easily slip off its surface. Corrosion testing and electrochemical measurements in 3.5 wt.% NaCl aqueous solution indicate that the Zn coating after OA passivation exhibits outstanding anti-corrosion properties compared with those exhibited by pure Zn coating. The corrosion products and mechanism of the two-layer coating were explored. This study shows that smooth metal oleate coatings can provide hydrophobicity and corrosion resistance simultaneously to mild steel substrates.