An initial investigation on the roughness and frictional properties of the self-assembled thin films frompolyelectrolytes is presented. Star-shaped C60-poly(styrene-maleic anhydride) was successful prepared. The multilayer thinfilms have been fabricated on mica with diazoresin as the cationic polyelectrolyte and hydrolyzed star-shaped C60-poly(styrene-maleic anhydride) as the anionic polyelectrolyte via self-assembly technique. The crosslinking structure of the films is formed from the conversion of ionic bond to covalent bond after UV irradiation.AFM/FFM investigations provide insights into the roughness and frictional properties on a microscale.The roughness depends strongly on the number of film layers in the case of C60-containing films.The frictional forces of the films exhibited a well behaved non-linear relationship in response to the change of applied load.It supports the prediction of enhanced load-bearing property of C60-containing thin films.