A "Janus" type of hexa- cata-hexabenzocoronene with three triptyceno subunits fused symmetrically on the periphery of coronene has been synthesized using a covalent self-assembly strategy. The triptyceno subunits form a nanosized nest on one side of the aromatic plane with space-matching fullerenes such as C60 and C70 to afford shape-complementary supramolecular complexes. The formation of the complexes in solution was confirmed by 1H NMR and fluorescence titration. Four complexes with C60 or C70 were obtained and studied by single-crystal X-ray diffraction analysis. In the crystal structure, the host shows a proper tunability to adjust its conformation in accordance with the shape of the guest. The different stoichiometric ratios and various stacking patterns of the complexes suggest the diversity of this nonplanar polyaromatic host in complexation with fullerenes.