A gas-phase radical rearrangement through intramolecular hydrogen-atom transfer (HAT) was studied in the glutathione radical cation, [γ-ECG]+., which was generated by a homolytic cleavage of the protonated S-nitrosoglutathione. Ion–molecule reactions suggested that the radical migrates from the original sulfur position to one of the α-carbon atoms. Experiments on the radical cations of dipeptides derived from the glutathione sequence, [γ-EC]+. and [CG]+., pointed to the glutamic acid α-carbon atom as the most likely site of the radical migration. Infrared multiple-photon dissociation (IRMPD) spectroscopy was employed to generate complementary information. IRMPD of [γ-ECG]+. in the approximately 1000–1800 cm−1 region was inconclusive owing to the relatively broad, overlapping absorption bands. However, the IRMPD spectrum of [γ-EC]+. in this region was consistent with the radical migrating from the sulfur to the α-carbon atom of glutamic acid. IRMPD in the 2800–3700 cm−1 region performed on [γ-ECG]+. is consistent with a mixture of both the original sulfur-based radical and the resulting glutamic acid α-carbon-based species. Comparisons are made with previously published condensed and gas-phase studies on intramolecular HAT in glutathione.