A superhydrophobic/superoleophilic Cu(OH)(2)-thioled film was fabricated by a simple chemical vapor corrosion method with thiol modification. The resultant can be applied to separate oil/water mixtures. Peculiarly, in the separation process, oil selectively permeated from water first, and then the water spontaneously passed through later, which can collect oil and water step by step without external energy. This is the first report describing the phenomenon as we know. It provides a new point of view for both theoretical research and industrial applications.