Recently they lithium vanadium bronzes have been ranked as the most promising cathode materials for nonaqueous and solid state rechargeable lithium batteries. In spite of their advantageous properties, relationships between the two basic kinds of gamma-Li-V bronze phases have not been investigated. Since these bronzes can easily form various oxygen and Li/V stoichiometries in the complex Li-V-O system, stoichiometric LiV2O5 bronze by solid state preparation techniques is difficult to achieve. From the V2O5-Li2O-V2O3 ternary system it was also recognized that the basic relation of gamma’-Li1+xV3O8 and gamma"-LiV2O5 phases is connected to their oxygen stoichiometry. Crystallized gamma"-LiV2O5 bronze powder was prepared from a YVO4-doped LiVO3 solvent system. This flux crystallization technique can produce better quality stoichiometric gamma’-LiV2O5 bronze phase (than previously reported methods) having more accurate crystallographic data, a = 9.6719 angstrom, b = 3.5992 angstrom, c = 10.6591 angstrom. During melting and subsequent solidification the incongruent melting gamma-LiV2O5 transforms into gamma’-Li1+xV3O8+LiVO3 phases.