Cauliflower-like polyaniline (PANI) was successfully prepared using an interfacial polymerization method. By modification with polydimethylsiloxane (PDMS) using chemical vapor deposition method, the surface wettability of cauliflower-like PANI can be tailored to be superhydrophobic with a water contact angle of 160.4°. The deposition of the low-surface-energy silicon coating originated from PDMS pyrolysis on the cauliflower-like PANI was confirmed by X-ray photoelectron spectroscopy and Fourier Transform Infrared Spectroscopy. The changes in thermal stability and conductivity of the as-prepared PANI before and after PDMS treatment were also investigated by thermogravimetric analysis and using a four-probe method. Compared with nanofiber-shaped PANI by electrodepositing polymerization, the PDMS-treated cauliflower-like PANI has superior surface wettability. Our study may open a new way for fabrication of superhydrophobic surfaces by developing novel nanostructured PANI. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014, 131, 39767.