Ion–molecule reactions between the neutral ethyl- (EF), isopropyl- (IF), t-butyl- (TF) and phenyl formate (PF) and proton-bound water clusters W2H+and W3H+(W = H2O) showed that the major reaction product is water loss from the initial encounter complex, followed ultimately by the formation of the protonated formate. Collision-induced dissociation breakdown curves of the formate–water complexes were obtained as a function of collision energy and modeled to extract relative activation energies for the observed channels. Density functional theory calculations (B3LYP/6-311+G(d,p)) of the water loss reactions were consistent with reactions having no reverse energy barrier in each case. Overall, the results indicate that the interaction of formates with atmospheric water can form stable encounter complexes that will dissociate by sequential water loss to form protonated formates.