The 266 nm photodissociation of gaseous CH3ONO has been studied by monitoring the OH (X-2 Pi) product using the single-photon LIF technique. The OH fragment has been found to be vibrationally cold and its rotational state distribution conformed to a Boltzmann distribution. The ratios of 2 Pi(3/2) to (2)Pi(1/2) of the OH fragment were found to be close to unity. The population in the Pi(-) state for the Lambda-doublets was dominant. An additional decay channel, yielding OH(X-2 Pi) fragments, has been observed and assigned to CH3O-NO + hv -> NO(X-2 Pi) + CH3O((XE)-E-2), CH3O((XE)-E-2) -> CH2OH((2)A) -> CH2(B-3(1)) + OH(X-2 Pi). (c) 2006 Elsevier B.V. All rights reserved.