This project involves controlling and characterizing the morphology of the active layer in a special type of organic photovoltaics (OPVs), consisting of porphyrin-fullerene composites, with emphasis on electron exchange interactions between the two components. The Vienna Ab Initio Simulation Package (VASP) is applied to model a variety of donor-acceptor complexes containing fullerene and porphyrin in terms of their stabilities as well as their geometric, electronic, and charge transfer features. The goal is to identify supramolecular chain structures with highest occupied molecular orbitals (HOMOs) and lowest unoccupied molecular orbitals (LUMOs) that may serve as electron (hole) transfer channels in a photovoltaic device. A stable structure, involving the planar adsorption of a porphyrin unit on a C60 hexagon, has been identified. The results for fullerene have been extended to phthalocyanine–fullerene dyads where the fullerene-derived unit Phenyl-C61-butyric acid methyl ester (PCBM) is connected to a porphyrin analogous electron donor through two oxygen-linked benzene rings. In both cases, the HOMO is located on the porphyrin segment, the LUMO on the fullerene component. As a fullerene, PCBM is a material of very high electron affinity, but it has better solubility properties than fullerene. It is often used in plastic solar cells or flexible electronics in conjunction with electron donor materials such as P3HT or other polymers. The results of our work contribute to the ongoing effort of using computational modeling to identify fullerene-based materials of potential relevance for organic photovoltaics.