Ferroelectric coupling effects on the energy-band structure of hybrid heterojunctions are investigated using hybrid photovoltaic devices with poly(3-hexylthiophene-2,5-diyl) (P3HT)/ZnO and poly(vinylidene fluoride-trifluoroethylene) (P(VDF-TrFE)). The self-organized P(VDF-TrFE): P3HT photoactive layer forms a novel architecture consisting of P3HT domains in a P(VDF-TrFE) matrix. The energy-band structure at the interface of the p-n heterojunction is tuned by artificial control of the ferroelectric polarization of the P(VDF-TrFE) material, consequently modulating the photovoltaic performance of the hybrid photovoltaic devices.