New photoelectron (PE) spectra of C6ClxF6-x- (x = 2, 3, 5) are presented and compared with previously reported PE spectra of C6F6- and C6ClF5-, along with the known properties of C6Cl6-. Based on a recent theoretical study [J. Phys. Chem. A 2024, 128, 8072-8079], anions of the mixed perchlorofluorobenzenes have competing molecular and electronic structures: one in which the electron is localized in a single C-Cl σ* orbital, resulting in a structure with a uniquely elongated C-Cl bond, and the other in which the excess charge is more delocalized, resulting in a more symmetric anion. In all cases, the experimental PE spectra are consistent with the former, with the exception of C6Cl5F-, the spectrum of which is not consistent with calculations on either structure. The adiabatic electron affinities of the neutrals are difficult to ascertain from the anion PE spectra because of vanishingly small signal near the origin. However, the vertical detachment energies are determined to be 3.20(10) eV for C6Cl2F4-, 3.09(5) eV for C6Cl3F3-, and 1.85(10) eV for C6Cl5F-. The VDEs of C6Cl2F4- and C6Cl3F3- are similar to the previously reported VDE of C6ClF5-, 2.95 eV [J. Phys. Chem. A 2024, 128, 5646-5658], and significantly higher than the previously reported VDE determined from the PE spectrum of C6F6-, 1.60 eV, measured on the same instrument [J. Phys. Chem. A 2023, 127, 556-8565]. To further benchmark the computational methods and gain insights into the relationship between the anionic structures in which the excess charge is localized in a single C-Cl σ* orbital and the delocalized structure, we measured the PE spectrum C2Cl4-, which exhibited a VDE consistent with the computed structure in which the excess charge is localized in a single C-Cl σ* orbital, and which was the computed lowest energy structure of C2Cl4-. We further explore the relationship between localized and delocalized structures in this molecular anion and C6Cl5F-.