Buckminster fullerene C-60 was used as a model to understand the attachment chemistry of large molecules on amine-terminated self-assembled monolayers (SAM) on semiconductor substrates. This type of interface serves as a prototype for future devices in such fields as solar energy conversion, biosensing, catalysis, and molecular electronics. Fullerene C-60 was attached to 11-amino-1-undecene self-assembled monolayers on a Si(111) surface. The chemical state and topography of the C-60-modified surface were characterized by surface analytical spectroscopic and microscopic methods and by computational investigation. X-ray photoelectron spectroscopy revealed that the secondary amine group is formed between the C-60 and the 11-amino-1-undecene SAM on the surface. The appearance of the pi-pi* C 1s shakeup peak confirmed the presence of C-60 on the surface. Infrared spectroscopic studies verified several characteristic features of the C-60 skeleton vibration and the 11-amino-1-undecene vibrational signature. The atomic force microscopy investigation suggested that the fullerene molecules produce surface features with an apparent height of similar to 2 nm and an average width of similar to 20 nm. A parallel study was performed on a Au(111) surface for comparison with the results obtained on the silicon substrate. The reaction between fullerene molecules and similar to 1% 11-amino-1-undecene diluted in decene SAM on the Si(111) surface accordingly yielded dilute and uniformly distributed C-60 molecules on the surface, which indicated that the amine groups were the reactive sites.