Several approaches have been employed to grow high-quality ZnSe epilayers on Ge/Ge0.95Si0.05/Ge0.9Si0.1/Si virtual substrates. The ZnSe epilayers were characterized by photoluminescence spectroscopy. Migration enhanced epitaxy and inserting an in situ thermal annealing ZnSe buffer layer effectively reduced the intensity of deep level emissions from the ZnSe epilayer grown on a 6°-tilted Ge/Ge0.95Si0.05/Ge0.9Si0.1/Si virtual substrate. Optimized conditions for growing high-quality ZnSe were used to deposit ZnCdSe/ZnSe multiple quantum wells on Ge/Ge0.95Si0.05/Ge0.9Si0.1/Si virtual substrates. Photoluminescence spectroscopy revealed quantum-confinement effect in the ZnCdSe multiple quantum wells. The evolution of the exciton emission peak energy and the linewidth as a function of temperature indicate a low density of localized sites in the sample with a well width of 1 nm. In the high-temperature regime, the thermal quenching of the excitonic emission intensity from ZnCdSe quantum well structures was governed by the thermal activation of carriers from quantum-well-confined states into barrier states.