This study presents synthesis and characterizations of two novel curved nanographenes that strongly bind with fullerene C60 to form photoconductive heterojunctions. Films of the self-assembled curved nanographene/fullerene complexes, which served as the photoconductive layer, generated a significant photocurrent under light irradiation. Gram-scale quantities of these curved nanographenes (TCR and HCR) as the crown sidewalls can be incorporated into a carbon nanoring to form molecular crowns, and the molecular structure of C60 @TCR is determined by single-crystal X-ray diffraction. The UV/Vis absorption and emission spectra, and theoretical studies revealed their unique structural features and photophysical properties. Time-resolved spectroscopic results clearly suggest fast photoinduced electron transfer process in the supramolecular heterojunctions.