Both nanoscience and nanotechnology have undoubtedly contributed significantly to the development of thermite-based nanoenergetic materials (NEMs) with tunable and tailorable combustion performance and their subsequent integration into devices. Specifically, this review article reflects the immense paybacks in designing and fabricating ordered/disordered assembly of energetic materials over multiple length scales (from nano- to milli-scales) in terms of realization of desired reaction rates and sensitivity. Besides presenting a critical review of present advancements made in the synthesis of NEMs, this article touches upon aspects related to various applications concomitantly. The article concludes with the author's summary of the insurmountable challenges and the road ahead toward the deployment of nanoenergetic materials in practical applications. The real challenge lies in the ability to preserve the self-assembly of fuel and oxidizer nanoparticles achieved at the nanoscale while synthesizing macroscale energetic formulations using advanced fabrication techniques both in bulk and thin film forms. Most importantly, these self-assembled NEMs have to exhibit excellent combustion performance at reduced sensitivity to external stimuli such as electrostatic discharge (ESD), friction and impact.