In this paper, the composite self-assembled super-hydrophobic film was prepared on copper surface with (3-mercaptopropyl)trimethoxysilane(MPTS) and octyltriethoxysilane(OS). The copper surface was etched in HNO3 (6.5 wt.%) solution before coated. The structure of composite film was analyzed by Fourier transform infrared spectra. Scanning electronic microscopy (SEM) indicated that the film had nano-micro scale structure. The contact angle reached 158.6°with sliding angle 3°, which suggested that the film was super-hydrophobic. The result of salt solution immersion test showed that anti-corrosion property of copper surface was greatly improved.