Organic materials which can self-assemble into higher-order superstructures have extensive applications in artificial light-harvesting systems, solution-processable bulk-heterojunction solar cells, and photofunctional devices owing to their unique charge transport properties. In this report, we demonstrate a self-assembled nonsymmetric donor–acceptor triad (TAN) composed of triphenylamine (T), anthracene (A), and naphthalimide (N) units, for achieving long-lived charge separation via aggregation. Steric hindrance imposed by diisopropyl groups of naphthalimide and the propeller-shaped triphenylamine unit obstructs planarization in TAN. The quantum theory of atoms in molecules demonstrated the presence of synergistic C–H···π, C–H···H–C, π–π, and C–O···O–C interactions between the adjacent TAN units in the crystalline state, leading to significant electronic coupling (Hab). The nonplanar geometry of the TAN triad in the monoclinic space group dictates a unique antiparallel arrangement between the adjacent TA...