AbstractThe protonation of 2,3‐ and 2,5‐dihydrofuran is examined in gas‐phase equilibrium proton transfer reactions conducted in an ion cyclotron resonance spectrometer. The thermodynamically favoured site of protonation in the two compounds is seen to be different: whereas the first isomer forms a carbocation upon protonation, the second isomer protonates on the oxygen atom to form an oxonium ion. The results obtained with substituted derivatives and with linear analogues confirm these conclusions. Molecular orbital calculations on the various structures for protonated bases are performed at the 4–31G level with correction for configuration interaction effects and at the 4–31G* level. The latter basis set provides the best results owing to the introduction of d‐type orbitals on the oxygen atom. The calculation results substantiate the experimental observations and provide details on the molecular structure of the protona