Based on Pauling's nature of chemical bond, the valence electron structures of TiN and FeAl have been constructed, and the relative electron density differences (REDD) between the low index plane of TiN and FeAl , respectively, have been calculated. [110] FeAl //[110] TiN crystallography orientation has been set up from the minimization of the electron density difference across the interface. From the viewpoint of improving the mechanical properties of composites, the formation of such structures must been engineered in the fabrication processing.