The ultraviolet photodissociation of nitrosobenzene at 266 nm has been performed on a universal crossed molecular beams machine with a TOFMS detector. The time-of-flight spectra of the NO and C6H5 photofragments have been measured. The TOF spectra evidence only one component. The measured photofragment translational energy distribution P(E-t) reveals that about 29% of the available energy is partitioned into translational energy. The anisotropy parameter beta at this wavelength is -0.64. From P(E-t) and beta, we deduce that during the photodissociation of C6H5NO, a perpendicular transition dominates over a parallel transition. Ab initio calculations were also performed to interpret the mechanism of the photodissociation.