The vibrational state distribution of NO formed in the radical–radical reaction N+OH→NO(v’≤9)+H; ΔH00=−204.0 kJ mol−1 has been determined using a pulse‐and‐probe technique. OH radicals were generated by pulsed laser photolysis of H2O2 at 266 nm in a flow of N2 which had been passed through a microwave discharge to produce N atoms. The vibrational distribution of NO, measured by laser‐induced fluorescence (LIF) spectroscopy, is similar to that predicted by phase‐space theory and corresponds to an average yield of ca. 31% of the energy available to the reaction products. Experiments in which LIF signals were observed as the pulse–probe time delay was varied showed that populations within different vibrational levels (v=0–8) displayed similar kinetics, consistent with rapid removal of NO(v) by reaction with N atoms, N+NO(v)→N2+O, at rates which exhibit a mild dependence on v.