Contactless electroreflectance (CER) has been applied to study optical transitions between the ground and excited states in polar and a-plane nonpolar 2 nm wide GaN/Al0.12Ga0.88N quantum well (QW) structures. In addition to the fundamental transition, CER features related to optical transitions between excited states were clearly observed for the polar QW structure whereas such features were not observed for the nonpolar QW structure. This experimental result clearly shows that the polarization-related electric field leads to a quantum confinement of some extra states in the polar QW system. Such states are not confined in the nonpolar QW and, therefore, optical transitions between them are not detected, i.e., only the fundamental transition is observed in CER spectrum of the nonpolar QW. (C) 2011 American Institute of Physics. [doi:10.1063/1.3533417]