The molecular mechanism for the cycloreversion of oxetane radical cations has been studied at the UB3LYP/6-31G* level. Calculations support that the cycloreversion takes place via a concerted but asynchronous process,where C−C bond breaking at the transition state is more advanced than O−C breaking. This allows a favorablerearrangement of the spin electron density from the oxetane radical cation (with the spin density locatedmainly on the oxygen atom) to the alkene radical cation which is one of the final products. Inclusion ofsolvent effects does not modify the gas-phase results.