A key requirement for realizing efficient organic photovoltaic (OPV) cells is the dissociation of photogenerated electron-hole pairs (singlet-excitons) in the donor polymer, and charge-transfer-excitons at the donor–acceptor interface. However, in modern OPVs, these excitons are typically not sufficiently harnessed due to their high binding energy. Here, we show that doping the OPV active-layers with a ferroelectric polymer leads to localized enhancements of electric field, which in turn leads to more efficient dissociation of singlet-excitons and charge-transfer-excitons. Bulk-heterojunction OPVs based on poly(3-hexylthiophene):[6,6]-phenyl-C61-butyric acid methyl ester are fabricated. Upon incorporating a ferroelectric polymer as additive in the active-layer, power conversion efficiencies increase by nearly 50%, and internal quantum efficiencies approach 100% – indicating complete exciton dissociation at certain photon energies. Similar enhancements in bilayer-heterojunctions, and direct influence of ferroelectric poling on device behavior show that improved dissociation is due to ferroelectric dipoles rather than any morphological change. Enhanced singlet-exciton dissociation is also revealed by photoluminescence lifetime measurements, and predicted by simulations using a numerical device model.