The threshold photoelectron, the threshold photoelectron photoion coincidence and ion breakdown spectra of trichloroethene and tetrachloroethene have been recorded from 9–22 eV. Comparisons with the equivalent data for the three dichloroethene molecules and theoretical calculations highlight the nature of the orbitals involved during photoionisation in this energy range. The ground electronic state of ( ) is bound, with excited valence states dissociating to ( ) and C2HCl+ ( ). Appearance energies suggest that C2HCl+ forms from by loss of two chlorine atoms, whereas forms from by loss of a Cl2 molecule. The translational kinetic energy release into ( ) + Cl is determined as a function of energy. In both cases, the fraction of the available energy released into translational energy of the two products decreases as the photon energy increases.