Reactive multilayer thin films are a class of energetic materials that continue to attract attention for use in joining applications and as igniters. Generally composed of two reactants, these heterogeneous solids can be stimulated by an external source to promptly release stored chemical energy in a sudden emission of light and heat. In this critical review article, results from recent investigations of these materials are discussed. Discussion begins with a brief description of the vapor deposition techniques that provide accurate control of layer thickness and film composition. More than 50 reactive film compositions have been reported to date, with most multilayers fabricated by magnetron sputter deposition or electron-beam evaporation. In subsequent sections, we review how multilayer ignition threshold, reaction rate, and total heat are tailored via thin film design. For example, planar multilayers with nanometer-scale periodicity exhibit rapid, self-sustained reactions with wavefront velocities up to 100 m/s. Numeric and analytical models have elucidated many of the fundamental processes that underlie propagating exothermic reactions while demonstrating how reaction rates vary with multilayer design. Recent, time-resolved diffraction and imaging studies have further revealed the phase transformations and the wavefront dynamics associated with propagating chemical reactions. Many reactive multilayers (e.g., Co/Al) form product phases that are consistent with published equilibrium phase diagrams, yet a few systems, such as Pt/Al, develop metastable products. The final section highlights current and emerging applications of reactive multilayers. Examples include reactive Ni(V)/Al and Pd/Al multilayers which have been developed for localized soldering of heat-sensitive components. (C) 2014 Published by Elsevier B.V.