The unimolecular fragmentation reactions of the radical cations of diethyl, diisopropyl, dipropyl, isopropyl propyl, and di(tert-butyl) peroxide have been investigated by mass spectrometric and isotopic labeling techniques. Two competing pathways for unimolecular decomposition in the Cls time regime (metastable ions) are observed: i) A combination of an alpha-C-C bond cleavage and a H migration gives rise to proton-bound dimers of two ketone or aldehyde molecules. ii) Ion/dipole complexes of alkyl cations and alkylperoxy radicals are generated by C-O bond cleavage. These complexes either exhibit direct losses of alkylperoxy radicals, or they rearrange via a coupled proton and H-atom transfer, this sequence of unprecedented isomerizations is completed by losses of alkyl radicals. Collisional activation experiments confirm that the ionic products of the latter process correspond to RR'C=OOH+; these ions can be regarded as protonated carbonyl oxides. In addition, we observe the elimination of alkenes leading to hydroperoxide radical cations and the expulsion of HO2. radicals. The latter process implies a C-C bond formation step between the two alkyl fragments leading to higher alkyl cations.