Star-shaped and leaf-shaped polyaniline (PAN!) hierarchical structures with interlaced nanofibers on the surface were successfully prepared by chemical polymerization of aniline in the presence of lithium triflate (LT). Chemical structure and composition of the star-like PANI obtained were characterized by FTIR and UV-vis spectra. PANI 20 architectures can be tailored from star-shaped to leaf-shaped structure by change the concentration of LT. The synthesized star-like and leaf-like polyaniline show good superhydrophobicity with water contact angles of both above 150 due to the combination of the rough nanoweb structure and the low surface tension of fluorinated chain of dopant. This method is a facile and applicable strategy for a large-scale fabrication of 2D PANI micro/nanostructures. Many potential applications such as self-cleaning and antifouling coating can be expected based on the superhydrophobic PANI micro/nanostructures. Crown Copyright (C) 2013 Published by Elsevier Inc. All rights reserved.