A novel super-hydrophobic film was prepared by myristic acid (CH3(CH2)12COOH) chemically adsorbed onto the polyethyleneimine (PEI) coated Fe3Al-type intermetallic wafer. The film character and structure were probed with contact angle measurement, scanning electron microscopy (SEM) and atomic force microscope (AFM). The results suggest that the structure of the film is similar to lotus and the seawater contact angle is larger than 150◦. Moreover, the corrosion resistances of untreated and modified samples in seawater were investigated by electrochemical impedance spectroscopy (EIS). Experimental results show that the corrosion rate of Fe3Al-type intermetallic with super-hydrophobic surface decreases dramatically because of its special microstructure.