AbstractThis work presents a synergy between organic electronics and supramolecular chemistry, in which a host–guest complex is designed to function as an efficacious electronic material. Specifically, the noncovalent recognition of a fullerene, phenyl‐C61‐butyric acid methyl ester (PC61BM), by an alternating perylene diimide (P)‐bithiophene (B) conjugated macrocycle (PBPB) results in a greater than five‐fold enhancement in electron mobility, relative to the macrocycle alone. Characterization and quantification of the binding of fullerenes by host PBPB is provided alongside evidence for intermolecular electronic communication within the host–guest complexes.