Thin films of GaNBi alloys with up to 12.5 at.% Bi were grown on sapphire using low-temperature molecular beam epitaxy. The low growth temperature and incorporation of Bi resulted in a morphology of nanocrystallites embedded in an amorphous matrix. The composition and optical absorption shift were found to depend strongly on the III:V ratio controlled by the Ga flux during growth. Increasing the incorporation of Bi resulted in an increase in conductivity of almost five orders of magnitude to 144 Ω-cm−1. Holes were determined to be the majority charge carriers indicating that the conductivity most likely results from a GaNBi-related phase. Soft x-ray emission and x-ray absorption spectroscopies were used to probe the modification of the nitrogen partial density of states due to Bi. The valence band edge was found to shift abruptly to the midgap position of GaN, whereas the conduction band edge shifted more gradually.