A facile strategy for growing the poly(2-hydroxyethyl methacrylate) encapsulated on the surface of SiO2 nanoparticles (SiO2/PHEMA) as a molecular host matrix for the luminescent Tb3+ via a combination of surface-initiated reversible addition fragmentation chain transfer polymerization and coordination chemistry was successfully developed. The structure, morphology and fluorescence properties of the materials were investigated using relevant physical and spectral techniques. The core-shell structure and uniform dispersion of SiO2/PHEMA and SiO2/PHEMA:Tb3+ complexes were found according to SEM and TEM analyses while their surface bonding characteristics were determined via FT-IR analysis. In photoluminescence measurement, the SiO2/PHEMA:Tb3+ nanoparticles showed characteristic emissions of Tb3+ with the strongest (D-5(4) -> F-7(5)) green emission without detectable emissions of ligands, demonstrating that SiO2 framework covalently bonded with PHEMA segments acting as an efficient matrix for sensitization of fluorescent Tb3+ ions.