Silica nanoparticles functionalized with polyvinylpyrrolidone (PVP) were obtained by the grinding/ mechanical activation of quartz or nonfunctionalized silica nanoparticles in a stirred media mill in the presence of 1-vinyl-2-pyrrolidone, as proven by Fourier transform infrared spectroscopy. The polymer layer thickness formed on the silica nanoparticles after 8 h of mechanical activation in the absence of polymerization initiators amounted to about 10 nm, as derived from shear rheology. The silica nanoparticles functionalized with the hydrophilic PVP by mechanochemical polymerization reaction were used as fillers for hydrogels based on poly(hydroxyethyl methacrylate) (polyHEMA). The water absorption, release properties, and mechanical properties of the polyHEMA-silica composites were measured as functions of the filler content and particle size of the filler. PolyHEMA samples containing 20 wt % of the functionalized silica particles exhibited a higher maximum water absorption than the unfilled polymer; this showed that the hydrophilic interface between the filler and the matrix improved the water absorption. The release of methylene blue from the poly-HEMA-silica composites was governed by diffusion and was almost unaffected by the silica particles. The values for the storage modulus and loss modulus of the poly-HEMA-silica composites increased with growing filler content. For constant filler content, the storage modulus increased with decreasing particle diameter of the filler; this showed that the reinforcing effect increased with the interface between the filler particles and the matrix polymer.