The nanometric organization of p-type and n-type materials is expected to facilitate charge mobility in OSCs, thereby preventing recombination and enhancing efficiency. Herein, the synthesis and self-assembly of monomers comprising one or two units of a TCAQ tweezer covalently connected to a fullerene derivative is reported. Such molecules self-assemble in solution (NMR) and on surfaces (AFM) to form linear and hyperbranched supramolecular oligomers, respectively. The self-assembly process was also found to have very little influence on the electronic properties of the electroactive units of the monomers (CV and UV/Vis), as was expected from their matching character. These polymers constitute two of the first examples of n-type supramolecular polymers reported to date.