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The valence ionization potentials of F2O and Cl2O have been determined by photoelectron spectrometry, and the results are compared with the predictions of ab initio and approximate LCAO SCF calculations. The first PES band shows vibrational structure which is assigned to ν1 for F2O, and to both ν1 and ν2 for (Cl2O). These frequencies all show slight increases over the corresponding values for the ground states of the neutral molecules.