The nature and impact of ZnO buffer layers on the initial stages of the hydride vapor phase epitaxy (HVPE) of GaN have been studied by x-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), x-ray diffraction (XRD) and photoluminescence (PL). During pre-growth heating, the surface ZnO layer was found to both desorb from ZnO-coated sapphire and react with the underlying sapphire surface forming a thin ZnAl2O4 alloy layer between ZnO and sapphire surface. This ZnO-derived surface promotes the initial nucleation of the GaN and markedly improves material surface morphology, quality and growth reproducibility.