Silica nanoparticles have been functionalized by click chemistry and atom transfer radical polymerization (ATRP) simultaneously. First, the silanized silica nanoparticles were modified with bromine end group, and then the azide group was grafted onto the surface via covalent coupling. 3-Bromopropyl propiolate was synthesized, and then the synthesized materials were used to react with azide-modified silica nanoparticles via copper-mediated click chemistry and bromine surface-initiated ATRP. Transmission electron microscopy, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, and thermogravimetric analysis were performed to characterize the functionalized silica nanoparticles. We investigated the enrichment efficiency of bare silica and poly(ethylene glycol) methacrylate (PEGMA)-functionalized silica nanoparticles in Pb(II) aqueous solution. The results demonstrated that PEGMA-functionalized silica nanoparticles can enrich Pb(II) more quickly than pristine silica nanoparticles within 1 h.