The precipitated characteristics of ␣ Љ-Fe 16 N 2 nitrides in the diffusion layer of ion-nitrided pure iron were investigated with transmission electron microscopy (TEM) and high-resolution electron microscopy (HREM). Three sets of ␣ Љ nitrides, whose habit planes are (100) ␣ , (010) ␣ , and (001) ␣ , respectively, do not precipitate simultaneously from the diffusion layer, which is different from the normal homogeneous precipitation in Fe-N alloys. Unlike the typical disc-shaped morphology reported widely, the ␣ Љ nitrides in the diffusion layer appear as ribbonlike slices. They grow on {001} ␣ matrix planes with a parallel orientation relationship, and the direction of their length is parallel to the ͗110͘ ␣ direction. The interface between the ␣ Љ nitride and ␣ matrix and a 7 deg [111]/(112) low-angle-tilt grain boundary in the ␣ Љ nitride were examined with HREM. The distributions of dislocations at the interface and the grain boundary were investigated. During microstructural examination, it was observed that a ␥ Ј-Fe 4 N nitride could grow on an ␣ Љ nitride directly. The orientation relationship during the ␣ Љ → ␥ Ј nitride transformation was determined as to be (001) ␥ Ј //(110) ␣ Љ , [110] ␥ Ј //[111] ␣ Љ .