The photodissociation dynamics of methyl nitrite (CH3ONO) was studied using 266 nm laser photolysis, and NO photofragments X (2)Pi nu(')=0,1,2,3) were probed by single photon laser-induced fluorescence spectroscopy. The ground vibrational state of the NO was found to be most populated, and the rotational distributions of each vibrational level were quite hot. The alignment A(0)((2)) between the electronic transition dipole moment involved in the absorption of the parent molecule and the rotational angular momentum J of the photofragment NO (v(')=0) was measured. Polarization experiments showed that the rotational angular momentum of NO was aligned perpendicularly to the transition moment of the parent molecule. The negative A(0)((2)) values and a preferential population of the Pi(-) doublet state revealed that the dissociation process has some characteristics of in-plane dissociation. (C) 2003 American Institute of Physics.