The monodisperse porous polysulfone (PSF) microspheres with hollow core/porous shell structure were prepared by a water-in-oil-in-water (W/O/W) emulsion solvent evaporation method. The morphology of PSF is investigated by using three different surfactants such as oleic acid, polyvinylpyrrolidone and polyoxyethylen(20)-sorbitanmonooleat. The prepared microspheres are developed as sorbents to remove oil from water due to their highly hydrophobic and superoleophilic properties. The PSF microspheres synthesized in the presence of oleic acid exhibit the best separation efficiency, which is 44.8 times higher than that of the pristine PSF powder. The microspheres with appropriate size, unsinkable properties, and excellent reproducibility can be quickly distributed and collected in seconds on the surface of water. The pore structure of PSF microspheres and interaction between oil and PSF are proposed to explain the high efficiency.