The paper describes a wet process for modifying the surface of polydimethylsiloxane (PDMS) using H2SO4/HNO3 solutions. The oxidation on the surface of PDMS was confirmed by the examinations of Fourier transform infrared spectrometry (FTIR), contact angle of water drop and X-ray photoelectron spectroscopy (XPS). The hydrophobic surface of pristine PDMS was not only changed to hydrophilic, but also formed wrinkles on it after chemical modification. Bilayer systems, stiff oxidized PDMS layers were capped on soft PDMS foundations, would generate easily compressive stresses due to the large difference in volumetric contraction rates and led to form wrinkles on the surface. Experimental results demonstrated the periodicity of wrinkles was controllable by controlling the duration of oxidation. Therefore, wrinkles could be arranged orderly by the guidance of external forces before oxidization. The potential technology for generating and ordering wrinkles on the PDMS surface is valuable in the applications of pressure sensors, biology, micro-optics and nano-/micro-fabrication in the future. (C) 2007 Elsevier B.V. All rights reserved.