Wurtzite AlN film is a promising material for deep ultraviolet light-emitting diodes. However, some properties that attribute to its crystal orientation, i.e., c-axis orientation, are obstacles in realizing high efficiency devices. Constructing devices with non-c-axis oriented films is a solution to this problem; however, achieving it with conventional growth techniques is difficult. Recently, we succeeded in growing a-axis oriented wurtzite heavily Fe-doped AlN (AlFeN) films via sputtering. In this article, we report the electronic structures of AlFeN films investigated using soft X-ray spectroscopies. As-grown films were found to have conduction and valence band structures for a film with c-axis in film planes. Simultaneously, it was found that large gap states were formed via N-p and Fe-d hybridization. To remove the gap states, the films were annealed, thereby resulting in a drastic decrease of the gap states while maintaining a-axis orientation. We offer heavy Fe-doping and post annealing as a new technique to obtain non-polar AlN films.