We report on the first example that applies coherent anti‐Stokes Raman scattering (CARS) to real time diagnostics of detonation products from a solid explosive. The supersonically expanding gaseous products, from the detonation of either lead azide pellets or powders, are studied, using broadband CARS. The density, and the rotational and vibrational temperatures of ground electronic state N2 molecules, N2(X), are monitored as a function of time at a fixed distance, 3.3 cm, from the azide surface. The rotational temperature is low, around 200–300 K, while the vibrational temperature is around 2000 K for delays of 8–12 μs, following the initiation of detonation. The density of N2(X), during this time interval, increases from ∼1×1017 to 1×1018 cm−3.