Using graphene oxide powder (GO), vanadium pentoxide(V2O5), oxalic acid(C2H2O4·2H20) and ammonium tungstate((NH4)10H2(W2O7)6)as raw materials, tungsten-doped vanadium dioxide /graphene composite were prepared by hydrothermal method. The effects of W doping and graphene oxide on the phase transition temperature and thermal conductivity of the composites were investigated. XRD, SEM, DSC, FTIR, and laser thermal conductivity measuring instruments were used to characterize the structural morphology and phase transition properties of composites. The results show that the agglomeration of vanadium dioxide particles is effectively improved after graphene compounding, and is uniformly compounded on the surface of graphene. When the atomic percentage of tungsten is 2.5% and the content of graphene oxide composite is 4% (based on the quality of V2O5), compared with the pure vanadium dioxide, the phase transition temperature of the tungsten Doped Vanadium Dioxide / graphene composite decreased from 68 ℃ to 32.2 ℃, and the thermal conductivity was increased from 0.700 W/(m·K) to 16.341 W/(m·K). The composite material can meet the requirements of good thermal insulation and high thermal conductivity at the same time, and overcome the unity of opposites between thermal insulation and heat dissipation.