Photovoltaics (PVs) benefitting from ferroelectric polarizations can overcome critical limitations of conventional type PVs. In this class, Bi2FeCrO6 is known to be the best-performing material; however, a fundamental understanding of the origin is lacking, which has limited further performance improvements. Here, we carried out a theoretical investigation of the electronic structure of this material. As a result, electron−hole ( e-h ) pairs are observed to separate upon photoexcitation, which can be a dominant underlying mechanism for the exceptional PV responses. Based on this understanding, we further suggest five novel materials that can offer a combination of strong e-h separations and visible-light absorptions. We expect the community of ferroelectric PVs to immediately benefit from the features of the new suggested materials.