Polystyrene (PS) composites reinforced with 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO)-oxidized cellulose nanofibrils (TOCNs) with various weight ratios were fabricated by casting and vacuum-drying mixtures of PS/N,N-dimethylformamide (DMF) solution and TOCN/DMF dispersion. TOCNs of 3 to 4 nm width were dispersed homogeneously at the individual nanofibril level in the PS matrix, such that the TOCN/PS nanocomposite films exhibited high optical transparencies and their tensile strengths, elastic moduli, and thermal dimensional stabilities increased with increasing TOCN content. Dynamic mechanical analysis showed that the storage modulus of the TOCN/PS films increased significantly with TOCN content above the glass-transition temperature of PS by the formation of an interfibrillar network structure of TOCNs in the PS matrix, based on percolation theory. The outstanding and effective polymer reinforcement by TOCNs results from their high aspect ratio, high crystallinity, and nanodispersibility in the PS matrix.