High boiling-point solvent additives, such as 1,8-diiodooctane, have been widely used to tune nanoscale phase morphology for increased efficiency in bulk heterojunction organic solar cells. However, liquid-state solvent additives remain in the active films for extended times and later migrate or evaporate from the films, leading to unstable device performance. Here, a solid-state photoactive molecular mediator, namely N(BAI)3, is reported that could be employed to replace the commonly used solvent additives to tune the morphology of bulk heterojunction films for improved device performance. The N(BAI)3 mediator not only resides in the active films locally to fine tune the phase morphology, but also contributes to the additional absorption of the active films, leading to ∼11% enhancement of power conversion efficiency of P3HT:PC60BM devices. Comparative studies are carried out to probe the nanoscale morphologies using grazing incidence wide-angle X-ray scattering and complementary neutron reflectometry. The use of 1 wt% N(BAI)3 is found to effectively tune the packing of P3HT, presumably through balanced π-interactions endowed by its large conjugated π surface, and to promote the formation of a PC60BM-rich top interfacial layer. These findings open up a new way to effectively tailor the phase morphology by photoactive molecular mediators in organic photovoltaics.