Formates are a class of organic molecules emitted into the atmosphere from fuel additives and industrial solvents. Formate-derived esters can undergo a vast range of chemical reactions in the atmosphere, most of which are initiated by oxidation by hydroxyl radicals. One potential reaction upon their interaction with atmospheric water is proton transfer to form protonated formates. The goal of the present work is to explore the dissociation of these protonated species and thus their possible atmospheric fate. Tandem mass spectrometry was employed to study the unimolecular dissociation of the protonated forms of methyl- (1), ethyl- (2), isopropyl- (3), tert-butyl- (4), and phenylformate (5). 1 and 2 lose CO as a common fragmentation product, forming a protonated alcohol, and 2 also generates neutral ethanol (forming protonated CO). 3 and 4 readily lose the stable isopropyl and tert-butyl radicals as well as neutral alkenes propene and isobutene. Methanol loss is also observed from both ions. 5 exhibits both phenyl radical loss (similar to 3 and 4) and CO loss (like 1 and 2). Density functional theory was used to explore the observed minimum energy reaction pathways for each ion, and CBS-QB3 single-point energy calculations provided reliable energetics.