A facile approach to a highly bio-active interface material is reported. XPS reveals that polar entities exist at the interface between PPAam and PPAac nanolayers. They induce strong dipolar orientation polarizability and cause the redistribution of charges, which results in a remarkable increase of polar surface energy and hydrophilicity of the multistack bipolar films. In particular bipolar films with amine groups on their outermost surface show strongly enhanced cellular mobility. The attachment, adhesion, proliferation, migration, and coverage of ECs are significantly enhanced on such films. They are therefore promising as vascular implant materials, and could have applications as coating materials for tissue engineering.