This article describes a simple stepwise layer-by-layer assembly method to fabricate a stable super-hydrophobic film based on urushiol. First, by means of the chelation between Cu(II) and the phenolic hydroxyl group in urushiol (U), urushiol-Cu nanoparticles (U-Cu) were obtained. Then, by the method of layer-by-layer assembly, a hydrophobic film with microstructure was prepared via hydrogen-bonding and coordination between U-Cu and PVP. After introducing S(2-) into the film, a novel micro- and nanoscale hierarchical superhydrophobic film with a water contact angle of 152 degrees was finally obtained. Due to the unique performances of urushiol, it is believed that the as-prepared surface can be used in the fabrication of chemical engineering materials at broad range. (C) 2011 Elsevier B.V. All rights reserved.