The photoionization and dissociative photoionization of chloropropylene oxide have been studied both experimentally and theoretically. In experiments, photoionization efficiency spectra for ions C3H5O+, CHO+, C2H4+, C2H3+, C2H2+, CH3+, and CH2OH+ were obtained. Theoretically, the energetics of the dissociative photoionizations were examined by ab initio Gaussian-3 calculations. The computational results are useful in our attempt to establish the dissociative photoionization channels of chloropropylene oxide. These proposed channels include six simple: bond cleavage reactions as well as a reaction involving intermediates and transition structures. The agreement between experimental and computational dissociation energies or barriers ranges from fair to excellent.