We have successfully fabricated triacetylcellulose (TAC) polymer-silica nanocomposite films having up to 40 wt % of incorporated silica nanoparticles by deliberately designing a surface ligand that has a structure similar to that of polymer repeating units and effectively modifying the surface of silica nanoparticles through chemical bonding. Cross-sectional TEM analysis reveals no significant aggregation in all TAC-silica nanocomposite films. Thermal analysis results suggested that TAG-silica nanocomposites had higher T-g and T-c values as compared to pure TAC, and the increase in T-g and T-c was affected by the silica content, The transparency of all the nanocomposite films was over 80% in the visible range, confirming the excellent compatibility of nanoparticles with TAC. In this study, we enhance the interaction between nanoparticles and polymer matrices by modifying the surface of nanoparticles with a ligand that has a structure similar to that of polymer repeating units. It is expected that this method can be applied to other polymer systems to develop useful nanocomposites.