The increasing demand for packaging materials calls for new technologies to achieve excellent thermal conductivity of polymer composites with low content of thermal conductive filler. This article prepared a kind of magnetically functionalized multilayer graphene (Fe 3 O 4 @MG) via electrostatic interactions, which efficiently enhanced the thermal conductivity of silicone rubber (SR) composites by the alignment of Fe 3 O 4 @MG in an external magnetic field. The morphology and structure of the Fe 3 O 4 @MG together with the thermal conductivity of corresponding Fe 3 O 4 @MG/SR composites were systematically investigated by SEM, TEM, XRD, elemental mapping, and thermal conductivity tester. The obtained results showed that Fe 3 O 4 @MG was induced to form chain-like bundles in silicone rubber matrix under the applied magnetic field, which enhanced the MG-MG interaction, and formed effective thermal pathways in the alignment direction. Furthermore, as coating mass ratio of Fe 3 O 4 @MG increased, the thermal conductivity of randomly oriented Fe 3 O 4 @MG/silicone rubber composites (R-Fe 3 O 4 @MG/SR) decreased gradually, whereas the through-plane thermal conductivity of vertically aligned Fe 3 O 4 @MG/silicone rubber composites (V-Fe 3 O 4 @MG/SR) increased even filled with same contents of thermal conductive filler.