Several bicyclo[3.2.1]oct-2-en-3-yl cations, as isomers of protonated 7-methyl- and 7-ethylcycloheptatriene and of the protonated C 8 H 10 and C 9 H 12 alkylbenzenes, respectively, have been studied by deuterium labeling and mass-analyzed ion kinetic energy (MIKE) and collision-induced dissociation/MIKE spectrometry. Labeling reveals that the bicyclic framework undergoes fast and apparently complete hydrogen equilibration prior to fragmentation, involving a series of skeletal and hydrogen rearrangements (1,2-C and 1,2-H shifts). Fragmentation of the bicyclic ions C 8 H 11 + and C 9 H 13 + is manyfold: It occurs in part by way of the isomeric alkylbenzenium ions, e.g. CH 3 CH 2 C 6 H 6 + and CH 3 C 6 H 5 CH 3 + , and C 2 H 5 C 6 H 5 CH 3 + and CH 3 CH 2 CH 2 C 6 H 6 + , respectively, with the corresponding 7-alkyldihydrotropylium ions as intermediates. Another fraction of the bicyclic ions does not fragment by way of alkylbenzenium ions but apparently by [5 + 2] cycloreversion of bicyclo[3.2.1]octenyl framework itself. This process is indicated by ethene expulsion associated with an unusually large kinetic energy release (T∗ ≈ 300 meV). The characteristic high-KER ethene loss was also found for protonated 7-ethylcycloheptatriene but not for protonated 7-methylcycloheptatriene, suggesting a delicate balance of the activation energies and confirming, in turn, that bicyclo[3.2.1]oct-2-en-yl cations are intermediates during the fragmentation of higher alkyldihydrotropylium ions.