Metal−organic chemical vapor deposition (MOCVD)-grown GaN on sapphire substrate was etched by hot phosphoric acids. Pyramid structures were obtained in the N-polar face of the MOCVD−GaN. Details of the formation process and morphology of the structures were discussed. The crystallographic plane index of the pyramid facet was calculated dependent on the symmetry of the wurtzite crystal structure and the tilt angle. The substrates with pyramid structures were utilized in subsequent hydride vapor phase epitaxy (HVPE) growth of GaN. Free-standing crystals were obtained, while HVPE-grown GaN achieved a certain thickness. Raman spectroscopy was employed to obtain the stress conditions of the HVPE−GaN without and with sapphire substrate. The mechanism of the self-separation process was discussed. This facile wet etching method may provide a simple way to acquire free-standing GaN by HVPE growth.