Developing a facile and versatile strategy for rapidly separating complex oil–water mixtures and collecting the oil content simultaneously is extremely important. Therefore, we report robust porous polydivinylbenzene (PDVB)–PDMS decorated superhydrophobic melamine sponge and filter membrane synthesis via a one-pot and environmentally friendly method. A firm hierarchically nanoporous coating was formed with the growth of PDVB cross-linking networks in situ on the substrates through polymerization in the presence of a PDMS adhesive. Compared with most oil absorbents suffering from limited absorption capacity and complicated oil recovery processes, the prepared superhydrophobic melamine sponges not only show repeated oil-sorption capacity but also can be used as oil-collecting devices to immediately collect oils in situ on a large scale from water surfaces. Thus, oil–water separation and oil collection were realized simultaneously via the facile oil-collecting device which significantly reduces ecological impact and loss of energy and simplifies oil-spill cleanup processes. Moreover, the decorated sponge exhibits mechanical and chemical stability, which is capable of separating complex oil/water systems (corrosive aqueous solutions, cold or hot water and even extremely turbulent water). Importantly, the porous polymer modified membrane is able to separate various surfactant-stabilized water-in-oil emulsions with a high separation efficiency.