Direct electrospinning of small molecules has great potential to fabricate a new class of fiber materials because this approach realizes the creation of various functional materials through the numerous molecular combinations. In this paper, we demonstrate a proof-of-concept to fabricate supramolecular fiber materials composed of cyclodextrin (CD)–fullerene inclusion complexes by electrospinning. Similar to the molecular state of fullerenes in solution, the resulting fibers include molecularly-dispersed fullerenes. We believe such a concept could be expanded to diverse host–guest complexes, opening up supramolecular solid materials science and engineering.