A convenient procedure was developed to prepare an ultra-thin film of supermolecules of a spherical fullerene C-60 and water-soluble azocalix[6]arene. The C-60 molecule is so hydrophobic that it easily forms a three-dimensional aggregate on the water surface. When C-60 molecules were spread on an aqueous solution of water-soluble azocalixarene that acts as a host for C-60, the hydrophobic C-60 was captured in the cavity of the host molecule at the boundary of two phases and formed amphiphilic supermolecules. The supermolecules assembled spontaneously into ultrathin films over 1-cm wide. The monolayer-like film could be transferred onto a solid support by the Langmuir-Blodgett technique or the inverse Langmuir-Schaefer technique. The morphology and the transferability of the supramolecular assembled films were examined by changing the host molecules, the initial density Of C-60 on the water surface, the subphase temperature and the metal ions in the subphase.