The mechanism of room-temperature (RT) intrinsic optical transition in high quality and purity GaN epilayer grown by metalorganic chemical vapor deposition (MOCVD) has been investigated. Our results show that the band-to-band instead of excitonic transition is the dominant transition in MOCVD grown GaN epilayer at RT. This conclusion is supported by the observation of the excitation intensity dependence of the photoluminescence emission peak position and by a model calculation. The band-to-band transition energy at RT at the limit of low carrier concentration has been determined to be 3.429 eV. Since the band-to-band transition is the dominant optical transition at RT, it thus suggests that the electron-hole plasma is most likely responsible for gain in GaN blue lasers similar to the case in other III–V semiconductor lasers. ©1997 American Institute of Physics.