The development of the oil industry brings the critical problem of ocean pollution by oil spill or fossil fuels. The use of materials for water/oil separation is one of the effective approaches to solve this crisis. Polyvinyl alcohol (PVA) has been used to prepare water/oil separation materials. Currently, glutaraldehyde has been employed as the cross-linking agent, which is well known to be toxic and environmentally unfriendly. Moreover, it is difficult to deal with the disposal of the Across-linked material. Here, we propose a strategy of fabricating macroporous material which was prepared by PVA and sodium silicate (Na2SiO3) in aqueous solution. Following through with the one-step method of sol-gel reaction of hydroxyl groups with trimethoxy(octadecyl)silane, the low surface energy substance was grafted on macroporous material and a super-hydrophobic macroporous membrane for water/oil separation was prepared. As oil sorbent, the as-prepared dried super-hydrophobic PVA/Na2SiO3 porous materials (PSD6S) have the adsorption capacity of 1.8-7.0 g/g for oil uptake, which depends on the type of oil liquid. Typically, the separation efficiency of this material could reach more than 99% even after 10 times of use without the help of ambient pressure. It is noteworthy that the as-prepared samples could be easily decomposable and dissolvable completely in acidic medium at a rapid rate.