We have measured anion photoelectron spectra of the diphenylphosphide anion, PPh2-, and its oxide, POPh2-, the former being a ligand which is often utilized in inorganic chemistry. From these spectra, we have determined the vertical detachment energies of these anions and estimates of the electron affinities of their corresponding neutral molecules. We also conducted computations that provided structures of both the anions and their corresponding neutrals in both systems as well as electron affinities and vertical detachment energies in both systems. The calculated electron affinities and vertical detachment energies are in good agreement with the experimental values in both systems. (C) 2014 Elsevier B.V. All rights reserved.