AbstractTime-resolved photoluminescence (TRPL) spectroscopy has been performed in the temperature range 2 K to 300 K on thick (300 μm – 1 mm) nominally undoped bulk HVPE grown GaN layers. The PL spectra are dominated by the free excitons (FEs) and the two neutral donor bound excitons (DBEs) at about 3.4712 eV and 3.4721 eV at 2 K, assigned to the residual O and Si donors, respectively. The zero-phonon decay curves for both FEs and DBEs are nonexponential, with a fast initial decay and a slower tail at longer times. The initial decay time of the FE is about 130 ps at 2 K in such samples, the corresponding initial decay time for the DBEs for O and Si is close to 300 ps. The different lines corresponding to the so called two-electron transitions for the DBE show a different behaviour, with a longer decay time than the corresponding principal DBE states. The LO phonon replicas of the DBEs also have a decay time in excess of 1 ns in lightly doped samples.