We report on recent optical investigations of free and bound exciton properties in bulk GaN. In order to obtain reliable data it is important to use low defect density samples of low doping. We have used thick GaN layers (of the order of 1 mm) grown by halide vapour phase epitaxy (HVPE) with a residual doping down to <1016 cm–3 in this work. With such samples all polarisation geometries could also easily be exploited. The influence of the surface states on the photoluminescence (PL) experiments is analysed, it is concluded that surface recombination plays an important role for the free exciton (FE) recombination. The electronic structure of the FEs is discussed in detail, including the influence of spin-exchange and polariton effects, and compared with polarised PL spectra at 2 K. The detailed structure of excited states from the PL spectra is discussed, but further data are needed to fully explain all the peaks observed. The polarized FE spectra at room temperature allow a determination of the bandgap as 3.437 eV at 290 K, assuming an exciton binding energy of 25 meV. The PL transient of the A FE is very short (about 100 ps) for the no-phonon (NP) line interpreted as dominated by nonradiative surface recombination. The longitudinal-optical (LO) phonon replicas of the A FE exhibit a longer decay of about 1.4 ns at 2 K, suggested to represent the bulk lifetime of the FE. The corresponding decay time at 290 K is 9 ns in our samples, a value that might be affected by nonradiative recombination. The Si and O donor bound exciton (DBE) spectra with sharp NP lines at 3.4723 eV and 3.4714 eV respectively, are well resolved together with the so-called two-electron transitions (TETs) and several optical phonon replicas. The electronic structure of the DBE states including excited rotational states is discussed and compared with experiment. The well-resolved TET lines allow an accurate determination of the ground state binding energy of the Si donor as 30.4 meV and 33.2 meV for the O donor. The PL transients of the DBEs reveal a non-exponential decay for the NP lines. The DBE NP transient lineshape is assumed to be influenced by optical dispersion and scattering in the vicinity of exciton resonances, as well as by surface effects. The DBE decay time can most properly be deduced from the PL decay of the respective TETs and LO replicas, leading to values in the range of 1.1–1.8 ns. These values differ significantly from previous theoretical predictions, where values about two orders of magnitude shorter were obtained. A tentative discussion of the main observed features of acceptor bound excitons (ABEs), which are much less studied in GaN, is given. A decay time of about 0.9 ns for the shallowest 3.466 eV ABE is estimated, i.e. shorter than that for the shallow donor BEs. (© 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim)