We report the growth of high-quality, smooth, and flat ZnO thin films on graphene layers and their photoluminescence (PL) characteristics. For the growth of high-quality ZnO thin films on graphene layers, ZnO nanowalls were grown using metal-organic vapor-phase epitaxy on oxygen-plasma treated graphene layers as an intermediate layer. PL measurements were conducted at low temperatures to examine strong near-band-edge emission peaks. The full-width-at-half-maximum value of the dominant PL emission peak was as narrow as 4 meV at T = 11 K, comparable to that of the best-quality films reported previously. Furthermore, the stimulated emission of ZnO thin films on the graphene layers was observed at the low excitation energy of 180 kW/cm2 at room temperature. Their structural and optical characteristics were investigated using X-ray diffraction, transmission electron microscopy, and PL spectroscopy.