The cathode material Li3V2(PO4)3/C composite is prepared by a sol spray-drying and post-calcining technology. XRD results show that the material is a well crystallized single phase. SEM and TEM observations reveal that the Li3V2(PO4)3/C powders have the spherical shape with a uniform particle size distribution from submicron to micron scale, and there is a homogenous carbon layer of 2.5nm thick on the particle surface. The tap density of Li3V2(PO4)3/C is as high as 1.61gcm−3. The electrochemical performance of the composite is excellent. At 0.1C rate, the Li3V2(PO4)3/C sample exhibits high initial discharge capacities of 127.41mAhg−1 between 2.5 and 4.3V, and 161.30mAhg−1 between 2.5 and 4.5V, respectively. Even at a rate of 10C, the composite can still deliver high discharge capacities of 102.27 and 111.64mAhg−1 in the potential regions of 2.5–4.3V and 2.5–4.5V, respectively.