The work aims to improve hydrophobicity of metal surfaces by proposing a method of preparing a controllable micro-nano structure on the surface of metal. Silk-screen printing could be used to prepare controllable fine patterns, electrochemical machining could be applied to process fine structures and chemical oxidation method could be utilized to prepare nanostructures. A super-hydrophobic surface with micro-nano composite structure was successfully prepared on the surface of copper. In this process, firstly ordered micro column array was prepared in the method of silk-screen printing aided electrochemical machining, and then a nanostructure was prepared in the surface of micro column in the method of chemical oxidization. Superhydrophobic property of the copper surface was characterized with scanning electron microscope (SEM) and based upon contact angle. Anti-frosting property of the copper surface was studied in mass variation method. Diameter of round mask film for silk-screen printing was 140~160 μm. After electrochemical machining, the column diameter was 130~140 μm, and height was nearly 15 μm. SEM test results showed that micro-nano composite structure appeared on copper surface which was etched in 15wt%FeCl3 solution. The maximum contact angle was 155° when fluoroalkylsilane ethanol solution was used to modify the machined surface, and the surface exhibited super-hydrophobicity. Moreover, it was also found that the anti-frosting property of the tested surface was significantly improved. The method of silk-screen printing aided electrochemical machining can be used to prepare microstructures in controllable shape and size, and micro-nanocomposite structures can be obtained by further processing the microstructures, which can form a superhydrophobic copper surface and has anti-frosting property.