A series of formate (methyl through butyl) and acetate (methyl through pentyl) esters have been protonated in the gas phase by the Brønsted acids H3+, N2H+, CO2H+, N2OH+, and HCO+. Carbonyl oxygen protonation is 87–97 kcal mol−1 exothermic for H3+ and 47–57 kcal mol−1 exothermic for the weakest acid HCO+, permitting a study of the effect of protonation exothermicity on the decomposition modes of the protonated esters. With the exception of protonated methyl formate, three decomposition modes, (a) to (c) are observed.[Formula: see text]Reaction (a) is unimportant for formates; for acetates it is the sole decomposition channel for the methyl ester, but is less important for higher acetates. The dependence of the relative importance of this reaction mode on the protonation exothermicity indicates an activation energy considerably in excess of ΔH0, presumably because the reaction involves a symmetry-forbidden 1,3-H shift for the carbonyl protonated ester. For the higher acetates where the difference in the proton affinities of the carbonyl and ether oxygens is less, acyl ion formation results, in part, from protonation at the ether oxygen. For protonated methyl formate the major fragmentation reaction yields CH3OH2+ + CO; this reaction also appears to have an activation energy considerably in excess of the ΔH0. For the remaining esters either reaction (b) or (c) is the major decomposition mode. The competition between these two channels depends strongly on the protonation exothermicity and the relative activation energies. From the reaction competition we conclude that 1,2-H shifts occur in the case of primary alkyl esters yielding more stable secondary or tertiary alkyl ions. This rearrangement appears to occur after the excess energy has been partitioned between the alkyl ion and the neutral acid since the extent of further fragmentation of the alkyl ion reflects the original structure of the alkyl group.