This work explores the formation of well-defined molecular p–n junctions in solution-processed self-assembled heterojunction solar cells using dodecyl­oxy-substituted contorted hexa­benzo­coronene (12-c-HBC) as a donor material and phenyl-C70-butyric acid methyl ester (PC70BM) as an acceptor. We find that the contorted 12-c-HBC molecules effectively assemble in solution to form a nested structure with the ball-shaped PC70BM. The result is a self-assembled molecular-scale p–n junction. When this well-defined p–n junction is embedded in active films, we can make efficient self-assembled solar cells with minimal amounts of donor material relative to the acceptor. The power conversion efficiency is drastically enhanced by the mode of donor and acceptor assembly within the film.