Neutron and X-ray reflection measurements and surface pressure isotherms of spread films of the fullerene—dodecylamine adduct C60[NH2(CH2)11CH3]x all indicate that this material may form monomolecular layers on water surfaces. The reflection data sets (neutron on both H2O and D2O) can be accounted for by a single model structure defined in terms of the dimensions of an average cell and its chemical composition.This model ascribes a total thickness of about 29 Å to the molecular interface layer with the following internal structure. The fullerenes (with several alkyl chains attached) form a central stratum and the remainder alkyl tails are located close to both the air and water interfaces. The alkyl moieties close to the aqueous substrate are hydrated. The reflection experiments and the isotherms suggest that on average 8 ± 3 dodecylamine molecules are present per fullerene, consistent within error, with elemental analysis 5 ± 2.By contrast, neutron reflection and surface pressure vs. area data of spread films of C60 fullerenes on aqueous surfaces indicate the formation of inhomogeneous multilayer films with a thickness and a surface roughness exceeding the molecular size. These underivatized fullerenes thus do not form monomolecular films.