The fabrications of single crystal films of ZnSe, ZnTe, In-doped ZnTe and ZnTe–ZnSe heterojunctions with graded energy band structure are reported. It is found that the growth rate of ZnTe and ZnSe are essentially limited by the molecular beam flux of constituent elements with smaller flux intensity than the other. Crystallographic and surface topograph investigations indicate the growth of single crystal film having smooth and flat surface. The photoluminescence spectra reveal intrinsic emission lines, which gives evidence of high quality of the epitaxial layer. The photoluminescence efficiency of ZnTe is improved by fabricating ZnTe–ZnSe heterostructure rather than depositing ZnTe on GaAs substrate.