Porous Li3V2(PO4)3/C (LVP/C) cathode materials have been synthesized via a sol–gel-combustion method. The porous LVP/C shows stable and extremely high rate capacity, owing to the special porous structure and the nano-sized particle. In the potential range of 3.0–4.3V, discharge capacities of 122, 114, 108 and 88mAhg−1 can be delivered at high rates of 10, 20, 40 and 60C after 100 cycles, respectively. In the potential range of 3.0–4.8V, the corresponding discharge capacities are 145, 129, 122, 114 and 103mAhg−1 after 500 cycles at 10, 20, 40, 60 and 100C, which is the highest level for LVP so far.