A novel cathode material for lithium-ion batteries, carbon-coated Li3V2(PO4)3 particles which anchored onto graphene sheets (Li3V2(PO4)3@C/graphene) have been prepared by a modified Pechini method. It is first proposed that the graphene oxide can act as a chelating agent in the reaction process. The nanocomposite is characterized by X-ray diffraction (XRD), scanning electron microscope (SEM), transmission electron microscopy (TEM) and element analysis. The composite shows excellent C-rate performance, delivered capacities of 104, 91 and 85mAhg−1 at 5, 30 and 50C in the voltage range of 3.0–4.3V, respectively. Moreover, the cycling performance is also improved in higher voltage range of 3.0–4.8V. The capacity retention is 83% with the capacity of 131mAhg−1 at 10C after 100 cycles. The outstanding features are desirable and enable the material to be an excellent cathode for lithium-ion batteries.