Photodissociation of gaseous nitroethane at 266 am has been studied by monitoring the NO((XII)-I-2) product using laser-induced fluorescence technique. Rotational state distributions of the NO(XZII(1/2) and (XII1/2)-I-2, v" = 0) photofragment have been measured and characterized by Boltzmann temperature of 810 +/- 100 K. Only the NO photoproduct in v" = 0 state can be observed in the present work. The geometries of the nitroethane, the ethyl nitrite and the transition state connecting the two isomeric structures have been investigated using ab initio method. The photodissociation dynamics of nitroethane is discussed on the basis of experimental observation and calculation results. (c) 2006 Elsevier B.V. All rights reserved.