An iron aluminide modified layer prepared by a novel powder mixed electrical discharge alloying (PMEDA) process with a green compact aluminum electrode is conducted to improve the corrosion performance of work pieces. The phase composition and microstructure of the modified samples are analyzed by Scanning Electron Microscope (SEM), Energy Dispersive Spectroscopy (EDS), X-ray Diffraction (XRD) and Transmission Electron Microscope (TEM). Corrosion performance is investigated by the electrochemical workstation and the mechanism of corrosion resistance improvement is explored. The 12A modified samples exhibit a hydrophobic 102.4° contact angle, while showing 669% and 40% less corrosion current density in the simulated aqueous corrosion condition in comparison with the non-treated and non-hydrophobic modified samples, respectively. These enhanced performances are attributed to the synchronization of a hydrophobic surface, corrosion-proof iron aluminide and a dense, well-distributed modified layer.