Understanding the dynamic responses of energetic materials is central to evaluating the energetic and chemical performance as well as development of novel energetic solids. These include thermal, mechanical and chemical processes in a relevant temporal (ns-to-μs) and spatial (atomistic-to-micro) scales. In this paper, we describe our recent developments of time-resolved characterization techniques capable of probing real-time structural and chemical evolutions across single event, metal combustions and intermetallic reactions. The methods utilize highspeed microphotography, spectro-pyrometry, and synchrotron x-ray powder diffraction and determine in-situ the particle sizes, temperatures and structures in μs time resolution. These timeresolved data provide insights into the fragmentation dynamics, thermal history, phase transitions, reaction mechanisms, and chemical kinetics governing these exothermic metal combustions and intermetallic reactions.