Li3V2(PO4)3 cathode material was prepared by spray drying and liquid nitrogen quenching method. The quenched sample, which is well crystallized with a single monoclinic Li3V2(PO4)3 phase, exhibits a slightly contracted lattice parameters a, b and c compared with the natural-cooled one. The sample shows rough similar-spherical particles in the size of 0.5–4μm, and its tap-density is as high as 1.64gcm−3. HRTEM results indicate that rapid quenching leads to the formation of a number of defects in Li3V2(PO4)3 crystals. Electrochemical tests reveal that the defects greatly improved the rate capability and cycle performance of Li3V2(PO4)3. The quenched sample delivers an initial discharge capacity of 124.1 and 113.6mAhg−1 at 2 C and 10 C rate, respectively, and shows the capacity retention of 97.6% and 93.4% after 100 cycles.