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Experiments demonstrate that peptides with ionization potentials (IPs) above 7.87 eV can be single-photon-ionized in the gas phase with a molecular fluorine laser following prior chemical derivatization with one of several aromatic tags acting as chromophores. 4-(Dimethylamino)benzoic acid, 1-naphthylacetic acid, and 9-anthracenecarboxylic acid (denoted Benz, Naph and Anth, respectively) behave as chromophores, allowing single-photon ionization for vacuum ultraviolet (VUV) laser light by lowering the IP of the tagged peptide. Anth-tagged peptides that are laser-desorbed from a substrate and subsequently postionized produce mass spectra dominated by the intact radical cation, although protonated ions and fragmented species are also observed. Electronic structure calculations on Anth-tagged peptides indicate that in addition to lowering the ionization potential, the presence of the aromatic tag increases charge localization on and delocalization across the ring structure, which presumably stabilizes the radical cation. Measurements on several tagged peptides confirm this calculation and show that the stabilizing effect of the tag increases with the size of the conjugated system in the order Benz < Naph < Anth. The tagged hexapeptide Anth-GAPKSC exhibits the parent ion, whereas the Benz- and Naph-tagged peptides do not. These results are supported by the experimental comparison of Anth-tagged vs untagged tryptophan, further suggesting that VUV postionization of tagged high-IP species is a promising method for expanding the capabilities of mass spectrometric analyses of molecular species.