Rhodium-catalyzed asymmetric ring-opening reactions of oxabenzonorbornadienes with aliphatic primary amines and substituted N-phenylpiperazines were investigated. These reactions are featured with the formation of a new carbon-nitrogen bond via an intermolecular allylic displacement of the bridgehead oxygen with amine nucleophiles, which offered the corresponding products in good to excellent yields (up to 97%) with excellent enantioselectivities (up to 99%ee).