Publication costs asslsted by Rockwell InternationalChemiluminescence from electronically excited BrF and IF has been observed from reactions of molecular halides (Br2, Iz, ICl, and HI) with OzF. Much more intense emission is produced by reactions of bromine or iodine atoms with OzF in the presence of excited singlet molecular oxygen. The emission spectra and photon yields of these reactions are consistent with a proposed mechanism in which the X + OzF reactions produce vibrationally excited ground state XFt molecules. These may cross to the A W , ) state (if sufficient energy is available) or be pumped to the B(3110+) state by collisions with excited singlet oxygen. In the reactions of molecular halides with OzF, halogen atoms may be produced via formation and decomposition of a triatomic complex.