Monoclinic lithium vanadium phosphate, Li3V2(PO4)3, has been successfully synthesized using LiF as lithium source. The one-step reaction with stoichiometric composition and relative lower sintering temperature (700°C) has been used in our experimental processes. The solid-state reaction mechanism using LiF as lithium precursor has been studied by X-ray diffraction and Fourier transform infrared spectra. The Rietveld refinement results show that in our product sintered at 700°C no impurity phases of VPO4, Li5V(PO4)2F2, or LiVPO4F can be detected. The solid-state reaction using Li2CO3 as Li-precursor has also been carried out for comparison. X-ray diffraction patterns indicate that impurities as Li3PO4 can be found in the product using Li2CO3 as Li-precursor unless the sintering temperatures are higher than 850°C. An abrupt particle growth (about 2μm) has also been observed by scanning electron microscope for the samples sintered at higher temperatures, which can result in a poor cycle performance. The product obtained using LiF as Li-precursor with the uniform flake-like particles and smaller particle size (about 300nm) exhibits the better performance. At the 50th cycle, the reversible specific capacities for Li3V2(PO4)3 measured between 3 and 4.8V at 1C rate are found to approach 147.1mAh/g (93.8% of initial capacity). The specific capacity of 123.6mAh/g can even be hold between 3 and 4.8V at 5C rate.