Deposition of an amorphous ZnTe seed layer with a thickness of 10 nm followed by its solid-phase crystallization was done before the beginning of molecular beam epitaxy of ZnTe layers on GaAs(1 0 0) substrates. RHEED patterns have proved that a creation of three-dimensional formations is avoided, and two-dimensional growth occurs during the early stage of epitaxy. Cathodoluminescence (CL) and X-ray measurements have evidenced a higher quality of ZnTe layers grown with an amorphous ZnTe seed layer. ZnTe substrates made of ZnTe crystals grown from vapor phase have been used for the epitaxy of ZnTe layers and ZnCdTe/ZnTe structures also. CL comparison of homo- and heteroepitaxial layers and structures shows the superiority of epilayers and structures grown on ZnTe(1 0 0) substrates.