A new fullerene derivative with an ammonium subunit has been prepared. Its ability to form supramolecular complexes with oligophenylenevinylene derivatives bearing one or two crown ether moieties has been evidenced by electrospray mass spectrometry, and UV-visible and luminescence spectroscopy experiments. Interestingly, the assembly of the C-60-ammonium cation with the oligophenylenevinylene derivative bearing two crown ether moieties leads to the cooperative formation of the 2:1 complex owing to intramolecular fullerene-fullerene interactions.