The paper reports the pulsed laser based photoacoustic pyrolysis technique to study the thermal stability of novel nitro-rich 1H-1,2,3-triazole derivatives of high energy materials (HEMs) for the first time. We have employed 532 nm wavelength, 7 ns duration pulses at 10 Hz repetition rate obtained from Q-switched Nd:YAG laser system to record the time resolved temperature dependent PA spectra in a specially designed PA pyrolysis system. The study has been carried out between the 30 and 350 °C temperature range. Thermally stable HEMs are insensitive to temperature and they release very small amount of volatile compounds such as H₂O, NO₂, and NO at high temperatures. The combined results obtained from PA and TG–DTA techniques open a new channel to understand the molecular dynamics of HEMs which is responsible for energy storage mechanism of these compounds in terms of free NO₂ at different temperature ranges. In addition, the experimental findings lead to develop a new tool to scale the efficiency of these molecules as a fuel.