The optical properties of Cd0.3Zn0.7S/ZnS strained‐layer superlattices grown on (100) GaAs substrates by low‐pressure metalorganic chemical vapor deposition, were investigated by means of photoluminescence excitation spectroscopy and through the effect of an electric field on exciton emission. A multiple longitudinal optical‐phonon emission process, related to the relaxation of excitons, has been observed for the first time in the excitation spectra. The localization of excitons has been found to be the dominant cause of the linewidth broadening. The effects on an axial electric field on exciton emission intensity and peak position have revealed that the dissociation of the localized excitons on the low‐energy side of the spectrum principally takes place due to impact ionization.