The effects of fluorine substitution on the Cope rearrangements of 1,5-hexadiene and 2,2'-bis-methylenecyclopentane have been examined computationally using (U)B3LYP/6-31 +G(d,p) and CASPT2/ 6-31 G(d) methodology. The calculations indicate that fluorine substituents at the hexadiene termini generally stabilize the transition states relative to the ground states of the chair conformations and destabilize pathways that occur via boat conformations, in accord with the experimental observations of Dolbier. With meso-2,2'-bis(difluoromethylene)cyclopentane, this destabilization is sufficient to favor a relatively dissociative concerted transition state resembling weakly interacting allyl radicals over a normal aromatic concerted boat transition state. This preference is due partly to an increase in the activation enthalpy for the concerted rearrangement coupled with the more favorable entropy for dissociation. In octafluoro- and decafluorohexadienes, the situation is reversed, and reaction through a cyclohexane-1,4-diyl is favored. Even in the octafluoro system with no radical stabilizing substituents at C(2) and C(5), the preference of fluorine for sp(3) centers causes reaction via the cyclohexane-1,4-diyl. In establishing methodology for this study, the conformations of 1,2-difluoroethane and 1,1,2,2-tetrafluoroethane were also examined thoroughly by the B3LYP method using three basis sets.