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 C2HCl3+ (C2Cl4+) is bound, with excited valence states dissociating to C2HCl2+ (C2Cl3+) and C2HCl+ (C2Cl2+). Appearance energies suggest that C2HCl+ forms from C2HCl3+ by loss of two chlorine atoms, whereas C2Cl2+ forms from C2Cl4+ by loss of a Cl2 molecule. The translational kinetic energy release into C2HCl2+ (C2Cl3+) + 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