A novel bilayer superhydrophobic film was constructed on Cu substrate by a simple multi-step process. First, (3-mercaptopropyl) trimethoxysilane (MPTMS) molecules were self-assembled onto the pre-etched Cu surface via covalent bonding followed by hydrolysis and condensation, then 1H, 1H, 2H, 2H-perfluorodecyltrichlorosilane (PFDTS) were grafted onto the resultant hydroxyl terminated surface via the Si-O-Si bonding. The so-prepared sample was defined as Cu-MPTMS-PFDTS. The structure and morphology of the samples were characterized by means of contact angle measurement, X-ray photoelectron spectroscopy and scanning electron microscopy. The corrosion behaviors of the films were evaluated by Tafel plot and electrochemical impedance spectroscopy on an electrochemical work station. The results indicated that the bilayer superhydrophobic film possessed better corrosion protection as compared with the control samples. The superiority of the corrosion protection was mainly ascribed to the following two aspects: the superhydrophobicity and polysiloxane micro-structures of the Cu-MPTMS-PFDTS. Copyright © 2012 John Wiley & Sons, Ltd.