The present study reports an effective approach of significantly enhancing electrothermal efficiency and shape recovery performance of shape memory polymer (SMP) nanocomposite, of which shape recovery was induced by electrically resistive heating. Metallic aluminum (Al) nanopowders synthesized from Al3+ solution were chemically grafted onto carbon fiber. Siloxane groups were grafted onto surfaces of the Al nanopowders to enhance the interfacial bonding between the carbon fiber and SMP matrix via van der Waals force and covalent bond, respectively. The siloxane modified Al surfaces could improve both the electrically induced shape recovery performance and electrothermal efficiency through facilitating the electrically resistive heating from carbon fiber into the SMP matrix. Effectiveness of the synergistic effect between siloxane modified Al surface and carbon fiber was demonstrated to achieve the electrical actuation for SMP nanocomposites at a low electrical voltage below 4.0 V.