ABSTRACTSingle crystalline ZnSe nanowires were fabricated on GaAs substrates by molecular beam epitaxy technique via Au-catalyzed vapor-liquid-solid reaction. The nucleation and initial growth of the nanowires were investigated by high-resolution transmission electron microscopy. It was revealed that Au catalysts initially reacted with the substrate forming binary AuGa₂ alloy droplets. The sizes of the catalysts determined the growth direction of ZnSe nanowires. A model based on the surface energies of the nanowire nuclei was proposed to explain the size dependence of growth direction for ZnSe nanowires.