A polarization modulation photoreflectance technique has been developed for optical characterization of semiconductor quantum confined structures. By using a tunable laser source in conjunction with polarization state modulation, a single beam modulation spectroscopy technique may be used to characterize the optical response of semiconductor materials and structures. Disclosed methods and instruments are suitable for characterization of optical signatures of quantum electronic confinement, including resolution of excitonic states at the band edge or other direct or indirect critical points in the band structure. This allows for characterization of semiconductor quantum well structures, for characterization of strain in semiconductor films, and for characterization of electric fields at semiconductor interfaces.