The effect of substituents on the rearrangement of vinylcyclopropane radical cation to cyclopentene was explored by density functional theory. Correlations have been established between the activation energy of the system and the nature, as well as the position, of the substituents. It was found that radical-or cation-stabilizing substituents in select positions reduce the activation energy for the rearrangement substantially, while activation energies for competing hydrogen shifts were largely left unchanged. We have identified positions in the vinylcyclopropane where substitution is necessary, and others that can be substituted less discriminately.