Low-energy acetol ions CH3C(=O)CH2OH•+, 1, dissociate to CH3C(H)OH+ and HC=O• by a double hydrogen transfer (DHT), a common reaction among oxygen-containing radical cations. Recent experimental work has shown that the isotopologue CH3C(=O)CH2OD•+ specifically loses HC=O• to produce CH3C(D)OH+. This finding refutes an earlier postulated attractive mechanism based on the behaviour of 1 in ion-molecule reactions. Using ab initio MO calculations (at the CEPA//RHF/DZP level of theory complemented with valence bond (VB) methods), a low-energy pathway was traced that may explain all of the available experimental observations. It is shown that the unimolecular chemistry of 1 can be understood in terms of two proton transfers, taking place in intermediate O•H•O and C•H•O bonded hydrogen-bridged radical cations. The two protons originate from the same moiety and a charge transfer complex is therefore implicated and shown to be involved. These concepts of proton and charge transfer may well be more generally applicable and they do correctly predict the unimolecular chemistry of ionized acetoin, CH3C(=O)CH(CH3)OH•+ and related α-ketols. Key words: ab initio calculations, hydrogen-bridged ions.