Carbon-coated monoclinic Li3V2(PO4)3 (LVP/C) cathode materials are successfully prepared via a polyvinylpyrrolidone (PVP)-assisted sol–gel method. LVP/C composites are investigated by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HR-TEM) and electrochemical methods. The results indicate that the sample synthesized with 9wt% PVP is coated with a carbon layer in a thickness of about 12nm, which presents excellent rate capability and good cyclic performance. In the potential range of 3.0–4.3V, it shows a capacity of 127.2 and 115.1mAhg−1 at 1 and 10C, respectively. Even at discharge rate of 20C, it still has 81.8mAhg−1 with 10.7% capacity loss after 120 cycles. The lithium diffusion coefficient of the as-prepared material is in the order of 10−8 cm2 s−1. Our experiment results demonstrate that the LVP/C composites prepared via a PVP-assisted sol–gel method can be an attractive candidate as cathode materials in high-power lithium-ion batteries.