A combination of IRMPD spectroscopy, collision-induced dissociation, deuterium isotopic substitution, and computational chemistry was used to determine the structure and unimolecular chemistry of [Zn(Pro-H)](+) and the singly hydrated complex in the gas phase. Five competing dissociation channels were observed: loss of H2O, CO, CO2, and HCOOH and the main fragmentation pathway, loss of neutral Zn. By comparing the IRMPD spectrum with the predicted IR spectra of the lowest energy structures, it was confirmed that [Zn(Pro-H)](+) complex is deprotonated at the amine moiety, and a hydrogen from either C2 or C5 migrated to Zn2+. In this H-type complex, ZnH+ was chelated between the amine nitrogen and the carbonyl oxygen. Calculations of the potential energy surface revealed that the loss of neutral zinc is energetically more favorable than the loss of dehydrogenated proline leading to ZnH+ product. Furthermore, calculations on all five primary decomposition routes, all beginning with the lowest energy structure, revealed that loss of Zn has the lowest energy requirement, consistent with it being the most abundant product of unimolecular dissociation following collisional or IR multiphoton activation. For the singly hydrated complex, [Zn(Pro-H)(H2O)](+), IRMPD spectroscopy confirms a structure with water added to the H-type structure and intramolecularly hydrogen bonded to the deprotonated amine site. This structure is not the lowest-energy [Zn(Pro-H)(H2O)](+) isomer, but it is the one where water is added to the lowest energy [Zn(Pro-H)](+) isomer.