The CO2 laser-induced dissociation of nitromethane (CH3NO2) is investigated through luminescence and laser-induced flourescence studies. The main reaction channel is found to involve fission of the CN bond. Both ground state and electronically excited NO2 molecules are produced. Emission from electronically excited diatomic fragments is also observed. Interesingly, at pressures below 0.5 Torr the CN* (B2Σ+ radical is produced unimolecularly. The mechanism of the fragmentation is discussed. © 1980.