Structural, electrical and optical properties of free-standing 200-μm thick GaN films grown by hydride vapor phase epitaxy (HVPE) have been investigated. After laser lift-off, the GaN substrates were mechanically polished on both Ga and N-sides and dry etched only on the Ga- side to obtain a smooth epi-ready surface. Hot H3PO4 chemical etching on both surfaces was used to reveal the defect sites, which appeared as hexagonal pits. The etched surfaces were then examined by atomic force microscopy. A few seconds of etching was sufficient to smooth the N- face surface and produce etch pits with a density of ≈ 1×107 cm−2. In contrast, a 50 minute etching was needed to delineate the defect sites on the Ga-face which led to a density as low as 5×105 cm−2. From plan-view and cross-sectional transmission electron microscopy (TEM) analysis, we have estimated that the dislocation density is less than about 5×106 cm−2 and ≈ 3×107 cm−2 for the Ga and N-faces respectively. The full-width at half-maximum (FWHM) of the symmetric (0002) X-ray diffraction rocking curve was 69 and 160 arcsec for the Ga and N-faces, respectively. That for the asymmetric (10 4) peak was 103 and 140 arcsec for Ga and N-faces, respectively. Hall measurements demonstrated very high mobility (1100 and 6800 cm2/V.s at 295 and 50 K, respectively) and very low concentration of donors (2.1×1016 cm−3) and acceptors (4.9×1015 cm−3). In the photoluminescence (PL) spectrum taken at 10 K, a rich excitonic structure has been observed with the highest peak attributed to the exciton bound to neutral shallow donor (BDE). The FWHM of the BDE peak was about 1.0 meV on the Ga face before and after hot chemical etching, whereas that on the N-face decreased from about 20 to 1.0 meV after chemical etching owing to the removal of the surface damage originated from the mechanical polishing.