The growth of ZnSe and CdTe thin films by close spaced sublimation is examined. The investigations show that ZnSe films deposited on glass substrates are polycrystalline and exhibit wurtzite-zinc-blende polytypism. The CdTe films grown on glass/SnO2/ZnSe are polycrystalline and have an f.c.c. zinc-blende structure as in the case of a glass/SnO2/CdS buffer layer. The electric and photovoltaic parameters of ZnSe/CdTe solar cells depend on the ZnSe film thickness. Furthermore, it is shown for the first time that the best photovoltaic parameters are achieved using a Zn buffer layer at the interface between ZnSe and CdTe.