AbstractThe HeI photoelectron spectra of the N‐oxides of the azanaphthalenes1–5and of the azaanthracenes6,7were ascertained. The inferred ionisation energies, and the assignments of the spectra, are presented and are discussed in respect to the electronic structures of the N‐oxides and the spectra of the azaderivatives. The data supports the description of the electronic structures of the basic heterocyclic N‐oxides based on PPP SCF calculations and the electronic abrosption spect