Six binary metal systems were selected to study the possibility of forming amorphous alloys by ion mixing or thermal annealing in multilayered Films, i.e. the Ta-Cu, Zr-Nb, Zr-Ta, Y-Zr, Y-Mo and Y-Ta systems, featuring positive heats of formation (ΔHf) ranging from +3 to +40 kJ/mol. Firstly, the interfacial free energy consisting of a chemical and an elastic terms was calculated and added to the energetic state of the multilayers. It was found that the excess interfacial free energy increased with increasing the fraction of the interfacial atoms in the multilayers, and could raise the multilayers to an energy level intersecting with or being higher than thai of the amorphous phase possessing a typical convex shape. It is therefore possible to produce amorphous alloys in such systems, if the multilayered filins included enough fraction of the interfacial atoms. The multilayered samples were then designed and prepared accordingly and both ion mixing and thermal annealing under appropriate conditions resulted in the formation of a number of new amorphous alloys, confirming the above prediction based on the interfacial free energy concern. It is noted that the success of synthesising amorphous alloys by solid-state reaction in the immiscible systems develops a new glass forming technique, namely interface-generated spontaneous amorphization, which has a great potential to produce new and relatively thick amorphous films, e.g. a Ta72Cu28 amorphous film of 800 nm thick was obtained.