This paper reports on the use of a 200 W, 10.6 μm CO2 laser for ignition of TNT (2,4,6‐trinitrotoluene) via heating. We used a high‐speed camera and silicon photodetectors to monitor the reaction. Ignition, here defined as a visible flame, occurred for laser powers of at least 100 W in combination with energies at least 50 J. However, self‐sustained ignition did not occur even with the ignition laser at 199 W with a total energy of 995 J.