A facile one‐step method has been developed to prepare both superhydrophobic and superoleophilic surfaces of polystyrene (PS) without any chemical modification. A rough film consisting of micro‐bead and nano‐fiber mixed structures is formed by spraying a PS solution onto a large area and any type of substrate. The mixed structures with such unique wettability properties can be used in oil/water separation and as oil sorbents.
