Gas phase He I and He II photoelectron spectra of the group 5 oxides P4O6, As4O6, Sb4O6, and P4O10 are reported. Qualitative descriptions of the electronic structure of these molecules are discussed with reference to ab initio molecular orbital calculations for the species P4, P4O6, and P4O10. On the basis of the experimental and theoretical results, correlations among electronic energy levels within the series (i) P4, P4O6, and P4O10 and (ii) P4O6, As4O6, and Sb4O6 are suggested. © 1980, American Chemical Society. All rights reserved.