The gas phase kinetics of group III elements such as gallium are important in potential chemically-driven energy-transfer lasers and in chemical vapor deposition processes in the electronics industry. Excimer laser photodissociation of volatile gallium compounds via multiple-photon processes provides, in principle, a convenient room-temperature source of gallium atoms for study using laser photolysis/laser-induced fluorescence techniques. In this paper, we report preliminary results on the production of atomic gallium from the multiple-photon dissociation of trimethylgallium at 193 nm. Prompt emission from a number of excited gallium states (5 2S, 4 2D, 6 2S, 6 2P°, 5 2D, and 4 4P) is observed. The time histories of the ground state (4 2P°1/2) and the metastable state (4 2P°3/2) have been measured using laser-induced fluorescence. The resulting time profiles are complicated even in the absence of an added reactant gas by the apparent production of ground state gallium at relatively long times (-10 μs) after the excimer laser pulse. Possible mechanisms for this (i.e., radical reactions to produce gallium, energy transfer, cascading from high lying metastable states, ionic processes, etc.) are being investigated. These results indicate that the photodissociation of trimethylgallium at 193 nm is complex. Mechanistic considerations suggest that photolysis at other wavelengths and with other precursors may lead to a cleaner source of gas-phase atomic gallium for kinetic studies, and these studies are in progress.