We have substantiated an organic photovoltaic cell (OPC) based on a novel concept where optical absorption due to the charge-transfer between different organic molecules is utilized. Research and development of OPC technologies have currently been conducted worldwide because the technologies are expected to realize light-weight, flexible photovoltaic sheets. In this study, we designed and fabricated a prototypical OPC using a molecular compound composed of two different kinds of organic molecules. It was found that the device presents a photovoltaic effect due to the irradiation of near-infrared light whose wavelength is longer than 1 μm, although such a photoelectric conversion of near-infrared light has been very difficult in conventional OPCs. Furthermore, the lifetime and the diffusion length of excitons or charge carriers in the device were found to be three orders of magnitude longer than those of the conventional OPCs. Based on the concept, we can expect to realize the more efficient conversion from light energy to electric energy.