Density functional theory calculations have been performed to study the diverse reactivity of pentaphenylborole toward different epoxides. We systematically investigated the effect of substituents on epoxides for the preference/competition of three experimentally observed pathways, that is, intramolecular proton transfer, direct ring expansion via insertion of one epoxide molecule, and ring expansion via insertion of two epoxide molecules. Our calculations also predicted a high competitivity between the proton transfer and direct ring expansion pathways for the epoxide containing both alkyl and aryl substituents.