The synthesis of trimethoxysilane end-capped linear polystyrene (PS), star-branched PS, and subsequent silicon (Si) surface modification with the linear and star polymers are described. Trimethoxysilane terminated PS was synthesized using sec-butyl lithium initiated anionic polymerization of styrene and subsequent end-capping with p-chloromethylphenyl trimethoxysilane (CMPTMS). Acid catalyzed hydrolysis and condensation of the trimethoxysilane end-groups resulted in star-branched PS. This is the first report of core-functionalized star-shaped polymers as surface modifiers and the first comparative study showing differences in surface topography between star and linear polymer modified surfaces. Comparison of polymer film properties to polymer dimensions in dilute solution revealed that the linear PS chains were in the intermediate brush regime and the star-branched PS produced a surface with covalently attached chains in the mushroom regime.