Fullerene molecules (C60) have been tethered to the surface of an azide-terminated self-assembled monolayer. Results obtained from water contact angles, ellipsometry, X-ray photoelectron spectroscopy, and UV-vis spectroscopy were consistent with the successful attachment of fullerene to the monolayer. Atomic force microscopy shows smooth, homogeneous areas of monomolecular films with a microroughness of 0.5 nm. In these monolayers, fullerene molecules are packed in an ordered lattice corresponding to the {h00} faces of a face centered cubic unit cell with edge length 1.4 +/- 0.1 nm.