Photoionization and photodissociation of tetrachloroethylene are investigated using positive and negative photoion mass spectrometry in the photon energy range 8–22 eV. Ionization energy (9.33 ± 0.05 eV) of tetrachloroethylene and appearance energies of fragment ions C2 , C2 , C, C2Cl+ and CCl+ have been determined from the photoionization efficiency (PIE) curves. In addition, the spectral structure assigned as a vibrational progression (v 2) at 13.48 eV is observed in the PIE curve of the parent cation. The preferred dissociation pathways near the threshold energies are proposed according to the present theoretical calculations (W1u) and the relative branch ratio computation. On the other hand, the negative ions 35Cl− and 37Cl− produced in the minor ion-pair dissociation channel are observed within the energy range. The dissociation pathways potentially related to the multi-body ion-pair dissociations are discussed with the help of the thermochemistry data obtained from the PIE spectra.