CO2 laser ignition experimental results are reported for the high‐nitrogen materials 3,6‐dihydrazino‐1,2,4,5‐tetrazine (DHT), 3,3′‐diamino‐4,4′‐azoxyfurazan (DAAF), and mixed N‐oxides of 3,3′‐azo‐bis(6‐amino‐1,2,4,5‐tetrazine) (DAATO3.5, where the “3.5” indicates the average oxide content) at a maximum irradiance level of approximately 140 W/cm2. Diagnostics include a photodiode, indium antimonide (InSb) IR detector, high speed (HS) video and a CO2 photodetector. “First light” is measured for DAATO3.5 and DAAF, however, due to the low visible light emission of the gas phase, thermal runaway, as measured by the InSb, is used as the ignition criterion for DHT. Ignition in the gas phase is captured by the high speed camera. It is observed that an increase in laser irradiance results in an increase in ignition and flame stand‐off distance for DAATO3.5. The high‐nitrogen material laser ignition results are compared to the common nitramine explosive, octahydro‐1,3,5,7‐tetranitro‐1,3,5,7‐tetrazocine (HMX). Laser ignition delays for the different high‐nitrogen materials are also compared in the context of Differential Scanning Calorimetry (DSC) data. It is determined that DSC onset temperature, while a rough indicator of ignition delay trends, is not the equivalent of a direct measure of ignition temperature.