Due to the non-equilibrium nature of deposition techniques, thin films can exhibit an energetic state far from thermodynamic equilibrium. Energy supply can stimulate a transition into other metastable states. Examples of metastable phase formation presented in this work are thermally stimulated solid state reactions in metallic nanometer Al/Co/Ni multilayers and phase formation and transition in metallic alloy films of the elemental materials system Fe-Cr. An interesting application illustrates the technical potential of metastable nanometer films.