In this work, we described an electrospinning process for creating superhydrophobic thermoplastic polyurethanes (TPU) mat with bead-on-string morphologies. The initially hydrophobic TPU electrospun film presented superhydrophobic trait after treatment with hydrophobic nanosilicas, which was prefabricated by refluxing nanosilicas in a toluene solution of hexadecyltrimethoxysilane (HDTMS). The relationship between the microstructures and wettability was also discussed. This superhydrophobic TPU film turned out to be benign materials for separating oil and water mixture. The development of the electrospun process described in this paper, as well as the extension of our method, will no doubt facilitate the achievement of other functional superhydrophobic films for various applications. (C) 2010 Elsevier B.V. All rights reserved.