In order to remove/collect oils from polluted water, polypyrrole (PPy) nanoparticles have been loaded onto different substrates (cotton, corn stalk, sawdust, metal, fabric and sponge) by in situ polymerization followed by further hydrophobic modification. A wide range of low surface energy reagent could be used, including cetylamine, dodecanethiol, stearic acid and hexadecyltrimethoxysilane (HDTMS). Observations showed that the as prepared superhydrophobic materials could effectively remove oil from water-in-oil emulsion and immiscible oil/water mixtures with separation efficiencies above 99.1%. The coated material exhibited outstanding resistance to abrasion, acids, bases, salt, high temperature water and long-term exposure in environment. The coating method suggested in this work provides a facile and efficient route for superhydrophobic material fabrication, which could be practically used for separation of oil/water mixtures under various harsh conditions.