We describe a method to form hydrophobic surfaces using PHBV (Poly (hydroxybutyrate-co-hydroxyvalerate))-a kind of intrinsically hydrophilic material. The concentration of polymer solutions was varied to control the surface morphology and resultant wetting property. The as-prepared films were characterized by micro-scale valley-and-hill structure, which was formed by aggregating of electrospun beads. The bead morphology changed from smooth to porous and popcorn-like with decreased concentrations. The shape of water droplet on these surfaces had contact angles ranging from 110.7 to 158.1 degrees, with a maximum standard deviation of 2.5 degrees. It was found that both the micro and nanostructure were important to create a superhydrophobic surface. (c) 2006 Springer Science + Business Media, Inc.