Bead-like nanocomposite Li3V2(PO4)3 (LVP) grown on carbon nanofiber (CNF) have been prepared by electrospinning and heat-treatment. The primary LVP crystals are squeezed together and grow outward because of the limitation of the reaction space for LVP precursors in PVP fiber, accompanying with the carbon nanofibers shrank in diameters. Compared with the traditional carbon-coated LVP, the combination of the “beads” (LVP nanoparticles) and the “string” (carbon fiber) are effective in conductivity and stability. A small amount of carbon content (5.27 wt%) in LVP/CNF is sufficient to enhance the rate performance and cycle ability. The initial discharge capacity of LVP/CNF is 196mAhg−1 at 0.1C, which is very close to the theoretical value (197mAhg−1) of pure LVP in 3.0-4.8V. In the long-term cycles at 20C-rate, LVP/CNF delivers the initial capacities of 127.5mAhg−1, and remains 102.0mAhg−1 at the 1000th cycle. Bead-like structure of LVP nanoparticles grown in carbon fibers is stable in thousands charge/discharge cycles at high current rate.