V2O5/Graphene composite material was prepared by a facile sol-gel method. The microstructure of the prepared sample was characterized by SEM, XRD, Raman spectroscope, and TGA. V2O5/Graphene // Li4Ti5O12 full-cell was assembled using the V2O5/Graphene composite and Li4Ti5O12 as cathode active material and anode active material, respectively. The results demonstrated that the V2O5/Graphene composite contained 0.55% graphene and had a two-dimensional sheet-like morphology with orthorhombic phase structure. Electrochemical characterizations revealed that the V2O5/Graphene composite exhibited higher lithium storage activity and better high rate capability than the pure V2O5 counterpart. At a current density of 200 mA/g, the V2O5/Graphene composite delivered a discharge capacity of 283 mAh/g, while that for the pure V2O5 was only 253 mAh/g; at a high current density of 5 A/g, the V2O5/Graphene showed a discharge capacity of 150 mAh/g, whereas that for the pure V2O5 was only 114 mAh/g. The charge transfer resistance of the V2O5/Graphene composite was142 Ω, which is much lower than that (293.3 Ω) of the pure V2O5 counterpart. In a voltage range of 1.0 V~2.5 V, the V2O5/Graphene // Li4Ti5O12 full-cell initially show a capacity decrease from 110 mAh/g to 96 mAh/g, then the capacity increases slowly and stabilized about 102 mAh/g in the 100th cycle; the coulomb efficiency during charge/discharge cycles is closed to 100%, suggesting the V2O5/Graphene composite is a promising cathode material for lithium-ion batteries.