This dissertation addresses nanoscale reactive multilayer films (RMFs) for the purpose of storing chemical energy as heat and supplying localized heat for joining and other industrial applications. Here, self-propagating reactions were analyzed for magnetron sputtered deposited binary Ti-Al, Zr-Al and ternary Ti-Al-Si RMF systems as a function of different Al-molar ratios, bilayer thicknesses and layer sequences. Reaction properties, namely reaction front velocity, temperature, and heat vary quantitatively over a wide range. The maximum reaction temperature of ~ 1800 °C has been achieved in ternary RMFs. This work also highlights the effects of oxidation and the unsteady propagation on the reaction properties. The scalability concept of RMFs was improved and ternary Ti/Si/Ti/Al RMFs were applied in the reactive joining. This dissertation provides new insights into multilayer modulation and opens more freedom to design ternary RMFs by controlling both, diffusion interfaces and distances. It is further shown that the development processes, simulation and experimental analysis are beneficial to design and to synthesize application tailored new RMFs.