The co-sputtered Cu-In precursor layers were characterized by bi-layer surface structure in which island-type crystals were formed in a small-crystalline matrix layer. The elemental composition of the island-type crystals corresponds to the compound CuIn2 and the matrix (area) consists of copper-rich Cu11In9 phase. The surface morphology of sequentially evaporated Cu-Zn-Sn precursor layers is determined by the deposition order of stacked consistent metal layers. Precursor Mo-Sn-Zn-Cu films exhibit a well-formed “mesa-like” structure of the surface in which larger crystals (about 1,5 μm) are located on a “small-crystalline” valley. For films with other sequences of metallic layers, the mesa like structure is not so well exposed and well formed flat precursor layers were produced replacing separate metallic Cu and Sn layers with Cu/Sn alloy layer. Selenization of both Cu-In and Cu-Zn-Sn precursor layers begins with the formation of binary Cu-selenides with compositions varying with the temperature. At temperatures higher than 3700C the selenization of Cu-In results in single-phase CuInSe2 films in contrast to the selenization of Sn-Zn-Cu films that results always in multi-phase films consisting of high quality Cu2ZnSnSe4 crystals and of separate small-crystalline phase of ZnSe.