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The spectral quantum yields of adenine, thymine, cytosine, and uracil films were measured at photon energies of 7 to 23 eV. In addition, photoelectron‐energy‐distribution measurements were made at 21.2 eV. The photoelectron spectra exhibit features which can be associated with density‐of‐states structures below the vacuum level. The difference between the observed photoemission threshold of a solid film and the calculated energy of the highest occupied orbital for the isolated molecule is found to be 1.5–2.0 eV.