A comprehensive study of the sub band-edge emission bands of AlxGa1-xN (0.06≤x≤1) thin films deposited on vicinal and on-axis 6H–SiC(0001) substrates is presented. At 4.2 K strong band-edge emission, ascribed to donor-bound excitons, shallow donor-shallow-acceptor pair emission, and a deep emission band associated with the “yellow” band of GaN, were observed via cathodoluminescence. The energy shift of the shallow donor-shallow-acceptor pair band with respect to the peak of the donor-bound excitons peak exhibited a less than one-to-one correspondence with increasing Al mole fraction due the increasing localization of either the shallow donor and/or shallow acceptor. The yellow band was observed for all compositions and exhibited a similar energy shift with respect to both the donor-bound excitons and the shallow donor-shallow-acceptor pair bands as the Al mole fraction increased, except for a brief decrease at x≈0.5. This decrease was attributed to a donor oxygen level which entered the band gap at approximately this composition. A strong, broad emission band observed at 3.25 eV at 295 K in AlN and commonly associated with oxygen impurities was shown to be closely related to the yellow band of GaN. © 1998 American Institute of Physics.