Transient resonance Raman spectra are reported for the CH3I-I species formed after ultraviolet photolysis of iodomethane in cyclohexane and acetonitrile solvents. The spectra display most of their Raman intensity in the overtone progression of the nominal I-I stretch mode and the C-I stretch fundamental. Density functional theory calculations were done for the CH3I-I species to help better understand its properties. We compare our results for the CH3I-I species to those previously reported for CH2I-I and find that the C-I-I geometry significantly influences the perturbation of the C-I bond and the chemical reactivity of the complex species.