Continuous‐wave and time‐resolved photoluminescence spectroscopies have been employed to study the band‐edge transitions in GaN epitaxial layers grown by plasma assisted molecular beam epitaxy. In addition to the neutral‐donor‐bound exciton transition (theI2line), a transition line at about 83 meV below the band gap has been observed in an epitaxial layer grown under a lower plasma power or growth rate. This emission line has been assigned to the band‐to‐impurity transition resulting from the recombination between electrons bound to shallow donors and free holesD0,h+). Systematic studies of these optical transitions have been carried out under different temperatures and excitation intensities. The temperature variation of the spectral peak position of theD0,h+) emission line differs from the band gap variation with temperature, but is consistent with an existing theory forD0,h+) transitions. The dynamic processes of theD0,h+) transition have also been investigated and subnanosecond recombination lifetimes have been observed. The emission energy and the temperature dependencies of the recombination lifetime have been measured. These results have provided solid evidence for the assignment of theD0,h+) transition and show that the motions of the free holes which participated in this transition are more or less restricted in the plane of the epitaxial layer at temperatures below 140 K and that the thermal quenching of the emission intensity of this transition is due to the dissociation of neutral donors. Our results show that time‐resolved photoluminescence spectroscopy can be of immense value in understanding the optical recombination dynamics in GaN. ©1996 American Institute of Physics.