In this paper, graphene-modified Li3V2(PO4)3 composites have been developed as Li-ion battery cathode materials with high specific capacity and excellent cycling stability. The composites are prepared by spray–drying process using graphene oxide nanosheet and citric acid as carbon source. X-ray diffraction patterns demonstrate that the as-prepared samples are well crystallized with orderly monoclinic structures. SEM and TEM images reveal that the 3D network graphene and Li3V2(PO4)3 primary nanoparticles interlace with each other. The citric acid-derived amorphous carbon species interrupt the stacking of graphene sheets and minimize in-plane anisotropy of electronic migration within graphene layers, which would facilitate fast electron migration and Li+ diffusion throughout the micro-sized spherical secondary particles. The discharge capacity of the composite could respectively achieve 131.4 and 181.5mAhg−1 in the voltage range 3.0–4.3V and 3.0–4.8V at 0.1C discharge rate, which almost reach the theoretical capacity of the cathode material. Both of them nearly showed no capacity decay at 0.1C charging and discharging rate after long cycles.