Electronically excited (4p2P½) and ground state (4p2P) bromine atoms, resulting from the flash photolysis of a number of simple bromides, have been observed using kinetic spectroscopy in the vacuum ultra-violet. The effect of wavelength on the primary processes has been investigated and has involved the use of vacuum ultra-violet flash photolysis. Br(42P½) was observed on photolyzing the molecules HBr, Br2, CHCl2Br and CF3Br but not from CH3Br, C2H5Br and CH2Br2. With HBr, the Lyman α transition of the hydrogen atom was also detected. The nature of the primary processes are discussed. The decay of Br(42P½) was measured in the photolyses of HBr and CF3Br. With the latter, the yield of electronically excited atoms on photolysis is sufficiently high for the deactivation by added gases to be determined. The deactivation cross-sections σ2 for CF3Br, HBr and Br2 were 4.5 × 10–3, 0.09 and 1.7 Å2, respectively.