Li3V2(PO4)3@C core-shell nanoparticles with typical sizes of 20-40 nm were synthesized using a hydrothermal-assisted sol-gel method. Ascorbic acid and PEG-400 were adopted as carbon sources and reductants. The uniform Li3V2(PO4)3@C nanocomposite obtained was composed of a Li3V2(PO4)3 core with high-phase purity and a graphitized carbon shell, which was characterized using XRD, SEM, TEM, and Raman analysis. The nanocomposite exhibited a remarkably high rate capability and long cyclability, delivering a discharge capacity of 138 mA h g(-1) at 5 C within a voltage range of 3-4.8 V and the capacity retention was 86% after 1000 cycles. The superior electrochemical performance of Li3V2(PO4)3@C indicates that it has potential for application as a cathode material in advanced rechargeable lithium-ion batteries.