This study investigates the unimolecular reactions of glutathione complexes with alkali metal cations in the gas phase through sustained off-resonance irradiation collision-induced dissociation and examines their structures using a combination of infrared multiphoton dissociation spectroscopy and computational techniques. Under soft CID conditions, glutathione complexes with charge-dense cations such as Li⁺, Na⁺, and K⁺ show significant fragmentation of glutathione, while complexes with heavier cations, Rb⁺ and Cs⁺, primarily undergo loss of glutathione. This behavior is attributed to the stronger non-covalent binding between smaller metal cations and glutathione, which competes with the dissociation thresholds of covalent interactions within the peptide complex. Using CREST, a tool for determining trial structures which were submitted to density functional theory calculations, a thorough investigation of the conformational space revealed many possible structures, including pentacoordinated structures for the Na⁺ and K⁺ complexes, as well as tetra-tri-, bi-, and monocoordinated structures along with zwitterionic structures for all metal cation/GSH complexes. For all alkali metal cation complexes, the thermodynamically most stable structures were found to be tetracoordinated A-type structures where the metal cation is bound to the amine nitrogen and three of the carbonyl oxygens-all except O2, the amide between glycine and cysteine. These computed infrared spectra for these lowest energy complexes were also consistent with the experimental vibrational spectra in the fingerprint region. Based on relative energies and the comparison of computed and experimental infrared spectra in the fingerprint region, the tetracoordinate A-type structures are concluded to be the dominant forms of the [M(GSH)] + complexes in the gas phase.