Crack-free bulk-like GaN with high crystalline quality has been obtained by hydride-vapor-phase-epitaxy (HVPE) growth on a two-step epitaxial lateral overgrown GaN template on sapphire. During the cooling down stage, the as-grown 270-μm-thick GaN layer was self-separated from the sapphire substrate. Plan-view transmission electron microscopy images show the dislocation density of the free-standing HVPE-GaN to be ∼2.5×107 cm−2 on the Ga-polar face. A low Ga vacancy related defect concentration of about 8×1015 cm−3 is extracted from positron annihilation spectroscopy data. The residual stress and the crystalline quality of the material are studied by two complementary techniques. Low-temperature photoluminescence spectra show the main neutral donor bound exciton line to be composed of a doublet structure at 3.4715 (3.4712) eV and 3.4721 (3.4718) eV for the Ga- (N-) polar face with the higher-energy component dominating. These line positions suggest virtually strain-free material on both surfaces with high crystalline quality as indicated by the small full width at half maximum values of the donor bound exciton lines. The E1(TO) phonon mode position measured at 558.52 cm−1 (Ga face) by infrared spectroscopic ellipsometry confirms the small residual stress in the material, which is hence well suited to act as a lattice-constant and thermal-expansion-coefficient matched substrate for further homoepitaxy, as needed for high-quality III-nitride device applications.