Rate constants and product ion branching fractions for the gas-phase reactions of O-2 and O-3 with the anions (a) PO2Cl-, (b) POCl3-, (C) POCl2-, and (d) PO2Cl2- were measured in a selected-ion flow tube (SIFT). The kinetics were measured at temperatures of 163-400 K and a He pressure of 0.4 Torr. Only PO2Cl- reacts with O-2 to a measurable extent, having k(163-400 K) = 1.1 x 10(-8)(T/K)(-1.0) cm(3) molecule(-1) s(-1), while O-3 reacts with all of the anions except PO2Cl2-. The fitted rate constant expressions for the O-3 reaction with anions a-c are as follows: k(a)(163-400 K) = 3.5 x 10(-6)(T/K)(-1.6), k(b)(163-400 K) = 4.0 x 10(-7)(T/K)(-1.2), and k(c)(163-400 K) = 3.7 x 10(-7)(T/K)(-1.4) cm(3) molecule(-1) s(-1). Calculations were performed at the G3 level of theory to obtain optimized geometries, energies, and electron affinities (EAs) of the reactant and product species, as well as to determine the reaction thermochemistry to help understand the experimental results. The POxCly- anions that have lower electron binding energies (eBE) and higher spin multiplicities are more reactive. The doublets are more labile than the singlets. How the extra electron density is distributed in the anion does not predict the observed reactivity of the ion. The reactions of PO2Cl- with O-2 and O-3 yield predominantly PO3- and PO4-. The reaction of POCl2- with O-3 yields mostly Cl- and PO2Cl2-, while the POCl3- reaction with O-3 yields mostly O-3(-) and PO2Cl2-.