We show that at the hetero-molecular interface, the molecular band offsets can be modified by either adjusting the dopant or dopant concentration of one or both molecular layers or by changing the dipole orientation at the intermolecular interface. Photoemission studies reveal the changes in electronic structure and diode devices exhibit conduction properties that are altered in response to changes to the molecular band offsets. As a demonstration, thin film copper phthalocyanine to crystalline ferroelectric copolymer poly(vinylidene fluoride with trifluoroethylene) heterojunction diodes, without additional dopants, are compared with doped polyaniline layers on the crystalline ferroelectric copolymer poly(vinylidene fluoride with trifluoroethylene). (C) 2008 Elsevier B.V. All rights reserved.