We prepared magnetic thin films Ni81Fe19on single-crystal Si(001) substrates via single graphene layer through magnetron sputtering for Ni81Fe19and chemical vapor deposition for graphene. Structural investigation showed that crystal quality of Ni81Fe19thin films was significantly improved with insertion of graphene layer compared with that directly grown on Si(001) substrate. Furthermore, saturation magnetization of Ni81Fe19/graphene/Si(001) heterostructure increased to 477 emu/cm3with annealing temperatureTa=400°C, which is much higher than values of Ni81Fe19/Si(001) heterostructures withTaranging from 200°C to 400°C.