Curved π-electronic molecules, dipyrrolylbenzodiazepines (dpbs), were synthesized via condensation of 1,3-dipyrrolyldiketones and phenylenediamines. Dpbs exhibited 1D hydrogen-bonding chains between pyrrole NH and diazepine N and the resulting packing structures in the solid state. The pyrrole and diazepine N sites coordinate RhI, providing curved π-electronic systems of increasing rigidity. Dpb underwent coassembly with C60, which was surrounded by a hydrogen-bonding ring structure of six dpbs. On photoexcitation, the coassembly exhibited ultrafast electron transfer from the dpb moiety to C60, depending on their proximal arrangement as well as electron-donating and -accepting properties.