In this paper, a series of Ce-doped Li3V2(PO4)3/C composite cathode materials for Li-ion batteries were synthesized by a facile and fast microwave assisted sol–gel route. The investigation of the influence of Ce doping on the structural and electrochemical characteristics of Li3V2(PO4)3/C shows that the resulting composite exhibits smaller particle size, lower electron-transfer resistance, and faster lithium ion migration, which are attributed to improved lithium ion transfer by the Ce doping. At low charge/discharge rates, the Ce-doped Li3V1.98Ce0.02(PO4)3/C composite delivers a stable specific capacity of ∼170 mAh g−1 for over 100 cycles. At high rates (e.g. 10C), the Ce-doped composite is still able to deliver stable capacities of up to ∼120 mAh g−1 which is ∼60% greater than its un-doped counterpart.