Proton transfer in dissociative protonation processes involving fluoroadamantane and other smaller model compounds with different reference bases has been studied, through the use of B3LYP density functional theory calculations. All systems investigated are characterized by single-well potential energy curves. Solvent effects on proton-transfer potential energies were studied by means of a self-consistent isodensity polarized continuum model (SCIPCM) approach. It was found that also in solution the proton-transfer potential is single-well. However, the effects of the solvent on the characteristics of the complex are not negligible. The distance between the heavy atoms, and as a consequence the position of the minimum, changes, and the well becomes less deep. For fluoroadamantane the proton transfer leads to the C-F bond fission, so that the equilibrium conformation corresponds to a tightly bound complex between adamantyl cation and hydrogen fluoride, solvated by one molecule of the corresponding reference base.