Ultraviolet photolysis of dibromoacetonitrile in cyclohexane solution was investigated using transient resonance Raman spectroscopy. The experimental Raman vibrational frequencies were compared to those predicted from density functional theory calculations for several probable photoproduct species. Our results indicate that significant amounts of the Br-NCCHBr adduct is produced on the nanosecond time scale. We briefly discuss the probable mechanisms of formation of the Br-NCCHBr species and implications for using substituted dihaloalkanes as carbenoid agents in cyclopropanation reactions.