A novel graphene–silicon dioxide hybrid (HGS) was prepared by plant polyphenol-tannic acid (TA) functionalized pristine graphene (G-TA) and primary amine-containing silane coupling agent modified SiO₂ (Si–NH₂). Through strong hydrogen-bonding interaction between the phenolic hydroxyl groups on G-TA and primary amine groups on Si–NH₂, SiO₂ was uniformly loaded to the surface of graphene. Due to the synergistic dispersion effect of graphene and SiO₂, which prevents restacking and re-aggregating of both graphene and SiO₂, HGS hybrids were distributed evenly in the natural rubber (NR) matrix (HGS@NR). Simultaneously, the surface roughness of graphene after loading SiO₂ and the interfacial interaction between the HGS hybrid and NR matrix were substantially improved. Due to the good dispersion and strong interface, the overall properties of HGS@NR nanocomposites are drastically enhanced compared with those of GS@NR nanocomposites prepared by dispersing the blend of unmodified graphene and SiO₂ (GS) in NR. The HGS@NR nanocomposites possess the highest tensile strength up to 27.8 MPa at 0.5 wt% and tear strength of 60.2 MPa at 0.5 wt%. Thermal conductivities of the HGS@NR nanocomposites were found to be 1.5-fold better than that of the GS@NR nanocomposites. Also, the HGS@NR nanocomposites exhibit excellent abrasive resistant capacity that is nearly 2-fold better than that of the GS@NR nanocomposites. These results suggest that HGS has great potential in high-performance nanocomposites and a new strategy of constructing the efficient graphene–SiO₂ hybrid fillers has been established.