High efficiency photo-induced dissociation (PID) has been demonstrated in a tandem time-of-flight mass spectrometer. This instrument focuses isomass ion packets to temporal and spatial dimensions similar to those of the focused laser pulses from a high power excimer laser. This high density overlap of photons and ions yields highly efficient fragmentation and also provides high resolution selection of specific precursor ion mass-to-charge ratio values. Using 193 nm photon excitation of the molecular ion of bromobenzene (m/z = 1561, fragmentation, collection, and PID efficiencies af 79%, 132%, and 104%, respectively, were obtained. Characteristic fragmentations of toluene, nitrobenzene, acetophenone, triethylamine, N,N-diethylformamide, N-methylacetamide, and cyclohexene have also been demonstrated.