A low-cost, high-oil-adsorption film consisting of polystyrene (PS) fibers is fabricated by a facile electrospinning method. Different fiber diameter and porous fiber's surface morphology play roles in oil adsorption capacity and oil/water selectivity. The results showed that oil adsorption capacity of PS oil sorbent film with small diameter and porous surface structure for diesel oil, silicon oil, peanut oil and motor oil were approximate to 7.13, 81.40, 112.30, and 131.63 g/g, respectively. It was higher than normal fibrous sorbent without any porous structure. The thinner porous PS oil sorbent also had excellent oil/water selectivity in the cleanup of oil from water.