Micro and nano rough cube copper crystals were prepared on a smooth copper substrate using a simple electrodeposition method. 1-Dodecanethiol/polydopamine multilayer films were self-assembled layer-by-layer on a modified rough copper surface. The surface contact angles of modified multilayer films could reach a maximum of about 154°, and the contact angles remained stable in air. A decrease in contact angle was observed after 35 d of immersion in seawater. Electrochemical impedance spectroscopy results showed that the corrosion resistance and chemical stability of super-hydrophobic films were superior to the hydrophobic surface obtained in a previous study, and the modified functional surface exhibited corrosion resistance ability.