Diiodomethane is an important halocarbon responsible for several atmospheric processes like ozone depletion and aerosol particle formation. Despite this, the thermochemical data and a detailed analysis of the pathways for the decomposition of this halomethane and its molecular ion [CH2I2](center dot+) are scarce In this paper an investigation of the photodissociation dynamics of the CH2I2 molecule focused on the I-loss-channel by the photoelectron-photoion coincidence (PEPICO) technique and computational methods is reported. The experimental results show that upon, VUV irradiation the dissociation of the lower electronic ionic states of diiodomethane leads only to the CH2I+ ion and the I atom. The theoretical calculations point out that isomeritation of [CH2I2](center dot+) into iso-diiodomethane [CH2I-I](center dot+) may Play an important role in the emission of iodine atom as compared to direct C-I bond breaking.