Solution-processed organic photovoltaic devices containing p-type and non-fullerene n-type small molecules obtain power conversion efficiencies as high as 2.4%. The optoelectronic properties of the n-type material BT(TTI-n12)(2) allow these devices to display high open-circuit voltages (>0.85 V) and generate significant charge carriers through hole transfer in addition to the electron-transfer pathway, which is common in fullerene-based devices.