The effect of the chain constraint on the glass-transition temperature of polystyrene (pS) was studied in the context of polymer tethering to curved surfaces. The synthesis and characterization of silica-graft-polystyrene (SiO2-g-PS) hybrid nanoparticles is reported. Silica nanoparticles possessing covalently bound pS chains were prepared by the atom transfer radical polymerization of styrene from functionalized colloidal surfaces. These hybrid nanoparticles serve as interesting examples of spherical polymer brushes, as a high density of grafted pS was achieved on the inorganic colloid. The confirmation of a brushlike extension of immobilized chains in a good solvent was obtained with dynamic light scattering in toluene of SiO2-g-pS colloids possessing various molar masses of tethered pS. The solid-state morphology of SiO2-g-pS ultrathin films was assessed with transmission electron microscopy, and this confirmed that the silica colloids were well-dispersed in a matrix of the tethered polymer. Differential scanning calorimetry was used to study the effects of tethering and chain immobilization on the glass-transition temperature of pS. The measured glass-transition temperature of annealed bulk films of the hybrid nanoparticles was elevated with respect to the value for pure bulk pS. The enhancements ranged from 13 to 2 K for SiO2-g-pS brushes possessing tethered pS with number-average molecular weights of 5230 and 32,670 g/mol, respectively.