A novel fluorescent nanohybrid complex comprising of SiO2 nanoparticles, poly(2-hydroxyethyl methacrylate) (PHEMA), and photoluminescent (Eu3+) was synthesized by a combination of controlled surface-initiated reversible addition fragmentation chain transfer (SI-RAFT) polymerization and coordination chemistry. Initially, PHEMA was grafted from the surface of SiO2 NPs by SI-RAFT and then reacted with succinic anhydride to provide carboxyl acid groups on the external layers of SiO2-PHEMA nanohybrids. The subsequent coordination of the nanohybrids with Eu3+ ions successfully afforded the photoluminescent Eu3+ tagged SiO2-PHEMA nanohybrid complex (SiO2-PHEMA-Eu3+). The structure and fluorescence properties of the Eu3+ coordinated nanohybrid complex were investigated using the respective physical and spectral studies.