The effect of the miscut angle of vicinal substrate on the optical and morphological properties of GaAs/AlxGa1-xAs quantum wells grown by metalorganic vapor phase epitaxy is studied by means of photoluminescence (PL) and atomic force microscopy. Within small changes of the miscut angle, we observe strong variations of the PL linewidth, energy, and lineshape, as well as transitions between the morphology of the sample's surface and interface. The relation between these features is discussed, and the particular case of structures exhibiting high optical quality is studied in more detail. Moreover, the role of growth dynamics is highlighted by observing the evolution of the hetero-interfaces during growth interruption.