Bilayer films of Bi and Sb with either a Bi or Sb layer at the surface are prepared by d.c. sputtering at room temperature. The results show that the surface layer grows epitaxially on the innermost layer and that the interface is sharp. The structure and morphology of the crystalline grains is found iu depend on the growth order, the grain size varying from several mu m to tenths oi nm. Interdiffusion is stimulated at the interface by laser-induced melting and when partial melting occurs, the non-melted material promotes epitaxial solidification. When melting of the whole layered structure is produced, the initial layer configuration is still found to have a strong influence on the morphology and structure of tile solid solutions Formed. The grain size varies in this case between hundreds of nm and a few mu m.