Discrete Fe‐N phases which are difficult to prepare by common chemical methods have been synthesized by rf sputtering. Some of these phases are relevant in the Fischer‐Tropisch synthesis of synfuels. Single Fe‐N phases as well as the desirable mixtures have been synthesized by a careful control of various sputtering parameters. These films showed varied columnar microstructure with the columns perpendicular to the film plane. Magnetic anisotropy measurements for selected samples containing pure Fe4N, &egr;‐Fe3N, and Fe4N+&agr;Fe have been carried out. The anisotropy components when the field (H) is perpendicular or parallel to the columns show significant differences in the magnetization versus H curves up to fields of 8 kOe at room temperature and evidence for superparamagnetism. These results are explained on the basis of structural anisotropy of the columnar structure of the films. Mo¨ssbauer results for the &egr;‐nitride film are compared with those reported in the literature and again related to the microstructure.