Micro-Raman spectroscopy was used to investigate the selective adsorption of methanol/water mixtures on the surface of [60] fullerene nanospheres. C60 molecules were dispersed in methanol/water mixtures with different methanol molar fractions ranging between 1 and 0.5. The Raman active pentagon pinch mode shifted significantly (±4 cm−1) as the mixture composition was changed. The shift in the Raman mode was sinusoidal in nature indicating that methanol then water is adsorbed preferentially on the fullerene surface at different mixture compositions. The observed behavior is attributed to structure forming effects of alcohol/water mixtures and the shape and size effect of fullerene surface.