Because the treatment of oily wastewater, generated from many industrial processes, has become an increasing environmental concern, the search continues for simple, inexpensive, eco-friendly, and readily scalable processes for fabricating novel materials capable of effective oil/water separation. In this study we prepared an eco-friendly superhydrophilic and underwater superoleophobic polyvinylpyrrolidone (PVP)-modified cotton that mediated extremely efficient separations of mixtures of oil/water and oil/corrosive solutions. This PVP-modified cotton exhibited excellent antifouling properties and could be used to separate oil/water mixtures continuously for up to 20 h. Moreover, the compressed PVP-modified cotton could separate both surfactant-free and -stabilized oil-in-water emulsions with fluxes of up to 23,500 L m-2 h-1 bar-1-a level one to two orders of magnitude higher than that possible when using traditional ultrafiltration membranes having similar rejection properties. The high performance of our PVP-modified cotton and its green, low-energy, cost-effective preparation suggest its great potential for practical applications.