Three fulleropyrrolidine derivatives, characterized by the presence of positive charges, were introduced in the interlayer space of montmorillonite. The composites were characterized by powder X-ray diffraction and differential thermal and thermogravimetric (DTA-TGA) analysis, in conjunction with FTIR, UV-Vis, Raman, and Fe-57-Mossbauer spectroscopies. Organophilic derivatives were intercalated into organically modified clays, while water-soluble fulleropyrrolidines were introduced into the clay galleries through ion exchange. The experiments, complemented by computer simulations, show that not all the clay-clay platelets are intercalated by the fullerene derivatives and that a sizable amount of charge transfer takes place between the host and the guests.