Spherical Li3V2(PO4)3/C cathode materials have been successfully synthesized by a spray drying method. The structure and morphology of the cathode materials are characterized with X-ray diffraction (XRD), scanning electron microscopy (SEM) and thermogravimetric (TG) analysis. The results show that synthesized monoclinic Li3V2(PO4)3 with high purities exhibits spherical morphology, in favor of enhancing the capacities and cycling stability of Li3V2(PO4)3/C cathode materials for lithium-ion battery. The Li3V2(PO4)3/C cathode materials sintered at 750 °C present best electrochemical performance among all the samples. It exhibits high initial discharge capacities of 99.2 mAhg-1 and capacity retention of 93.6% after 200 cycles at a rate of 1C within a voltage range of 3.0–4.3 V.