Regulating the interfacial interaction between fillers and matrices is crucial for fabricating high-performance polymer composites. In this research, a functionalized core-shell hybrid silica@graphene oxide was produced by the charge attraction method, and then added to a trans-1,4-polyisoprene matrix as a neoteric filler to obtain a brand-new silica@graphene oxide/trans-1,4-polyisoprene polymer nanocomposite. The hybrid incorporation simultaneously improved the fracture toughness, mechanical strength and heat resistance of the nanocomposites. We examined the thermal, mechanical and shape memory properties of the nanocomposites via methodical measurements from the microscale to the macroscale. The experimental results demonstrated that, compared with other samples, the nanocomposite sample with 1.0 wt% silica@graphene oxide exhibited the best mechanical and thermal performance, and the fabricated nanocomposites showed good shape memory properties. This new and feasible approach is likely to enable a new strategy for the design of interfaces for developing nanocomposites with high performance.