Time‐resolved optical emission spectroscopy, with a resolution of ≂10 ns, was used to investigate the formation of excited photofragments during pulsed ArF excimer‐laser irradiation of gaseous aluminum bromide. The solid Al2Br6source was maintained at 50 °C and Ar used as a carrier gas to provide an aluminum bromide partial pressure of ≂3×10−6Torr (4×10−4Pa). The total pressure in the reactor was typically 300 mTorr (40 Pa). Following the laser pulse, emission was observed from the Al 4s 2S1/2→3p 2P1/2and 4s 2S1/2→3p 2P3/2transitions at 394 and 396 nm, respectively. The decay of the Al emission intensityIAlwas convoluted with the temporal shape of the excitation pulse since the radiative lifetime of the Al 2Sstate, 6.8 ns, was less than the laser pulse width, ≂20 ns. The rise time ofIAl, on the other hand, was<10 ns, indicating that Al was formed photolytically rather than through subsequent collisions involving photofragments.IAlvaried with the ArF laser intensityIhνasIAl∝I2hνforIhν≲4.5 MW cm−2andIAl∝Ihνat higher laser fluences. Raising the source gas temperature to increase the AlBr3to Al2Br6ratio in the feed gas, at constant total pressure, dramatically increasedIAl.