Frequent oil spill accidents and industrial wastewater discharge has always been one of the most severe worldwide environmental problems. To cope with this problem, many fluorine-containing and high-cost materials with superwettability have been extensively applied for oil-water separation, which hinders its large-scale application. In this work, a novel human hair fiber (HHF)-polymerized octadecylsiloxane (PODS) fiber was fabricated with a facile one-pot dip-coating synthesis approach, inspired by the self-assembly performance and hydrophobicity of OTS modification. The benefits of prominent hydrophobic/lipophilic behavior lie in the low surface energy, and a rough PODS coating was rationally adhered on the surface of HHF. Driven solely by gravity and capillary force, the HHF-PODS showed excellent oil/water separation efficiency (> 99.0%) for a wide range of heavy and light oil/water mixtures. In addition, HHF-PODS demonstrated durability toward different harsh environments like alkaline, acid, and salty solutions.