AbstractNano titania (nTiO2) aggregated graphene oxide (GO) hybrid nanostructures were successfully prepared by employing 3‐(Aminopropyl) triethoxysilane (APTES)‐modified nTiO2 as precursor material. The resulting self‐assembled core‐shell hybrid structure was observed to have hierarchical porous structure with nTiO2 forming the core and GO forming the shell in accordance with transmission electron micrographs. The mechanical properties of the hybrid composites were compared with that of individual GO and nTiO2 loaded systems and improved performance was observed. The incorporation of the hybrid filler improved the fracture toughness of epoxy composites by about 200%, which is indeed significant. Hence, this novel approach of employing self‐assembled APTES modified nTiO2 agglomerated GO hybrids as filler in epoxy was found to be beneficial in enhancing the toughness of epoxy.