Photoluminescence and Raman scattering spectra in CdTe/ZnTe heterostructures and superlattices with narrow quantum wells (4.8–9.2 A) in a temperature range of 5–300 K have been measured. The temperature dependences of the intensity of exciton luminescence in isolated quantum wells have been studied, and the thermal activation energies associated with the effective barriers for electrons and holes have been determined. In CdTe/ZnTe heterostructures, the binding energies of an exciton with a heavy hole have been determined as functions of the quantum well width. The multiphonon Raman spectra that exhibit distinctive features, such as the weak intensity of nLO phonon lines of ZnTe (n 2), and the multiple participation in scattering of acoustic LA phonons with large wave vector, have been investigated. The results have been explained based on the concept of the relaxation of hot excitons over the exciton band.