The ultraviolet (UV) photodissociation dynamics of methyl iodide at 333.45 nm has been studied using resonantly enhanced multiphoton ionization in conjunction with a time-of-flight mass spectrometer (REMPI-TOFMS). At this wavelength methyl iodide photolysis involves a transition with significant parallel and perpendicular character. Both ground (I) and spin-orbit (I*) excited iodine result from a parallel transition to the (3)Q(0) state. In contrast, the perpendicular transition, which most likely involves initial excitation to the (3)Q(1) state, leads exclusively to production of I. Based on data from this study, an upper limit for the conical intersection between the (3)Q(0) and (1)Q(1) potential surfaces is 30 500 cm(-1).