Molecular self-assembly is considered as a promising way to control the manufacture of new materials and their integration into hybrid devices with novel properties. In this work the authors have synthesized a fulleropyrrolidine bearing a phenylacetylene moiety via the Prato reaction. The characterization of the fulleropyrrolidine by nuclear magnetic resonance and optical spectroscopy is reported, and its self-assembly by crystallization study has been investigated according to the used solvents. If the solvent that effectively solubilizes fullerene derivative is tetrahydrofurane, the nano-square plates with 1-3 um in length and 50-100 nm in thickness are fonned, while if the solvent is toluene, 5 um diameter 'nano-flowers' are obtained.