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We report a flame retardant epoxy nanocomposite reinforced with 9,10-dihydro-9-oxa-10-phosphaphenantrene-10-oxide (DOPO)-tethered SiO₂ (DOPO-<i>t</i>-SiO₂) hybrid nanoparticles (NPs). The DOPO-<i>t</i>-SiO₂ NPs were successfully synthesized through surface treatment of SiO₂ NPs with (3-glycidyloxypropyl)trimethoxysilane (GPTMS), followed by a click reaction between GPTMS on SiO₂ and DOPO. The epoxy nanocomposites with DOPO-<i>t</i>-SiO₂ NPs as multifunctional additive exhibited not only high flexural strength and fracture toughness but also excellent flame retardant properties and thermal stability, compared to those of pristine epoxy and epoxy nanocomposites with a single additive of SiO₂ or DOPO, respectively. Our approach allows a facile, yet effective strategy to synthesize a functional hybrid additive for developing flame retardant nanocomposites.