A 20.5 period distributed Bragg reflector stack based on AlN/GaN has been grown on (0001) sapphire by electron cyclotron resonance plasma-assisted molecular-beam epitaxy. Peak reflectance up to 95% was observed at a wavelength of 392.5 nm. Cross-section transmission electron microscopy studies indicate that the interface of GaN-on-AlN is always sharper and more distinct than the interface of AlN-on-GaN. This is attributed to the different growth modes of AlN and GaN. When AlN grows on GaN, it tends to grow in a two-dimensional mode (Frank–van der Merwe mode) whereas GaN grows on AlN in a three-dimensional mode (Stranski–Krastanov mode). Based on these findings, the experimental reflectance data were simulated using the transmission matrix method. © 1999 American Institute of Physics.