The mechanochemical activation method has been used in order to reduce the synthesis times and temperatures for oxides in the system Bi-V-O-2. This new synthesis procedure yields to the formation of amorphous powders of 2Bi(2)O(3):V2O5 and Bi2O3:VO2 compositions. Annealing at low temperatures results in the stabilization at room temperature of the high temperature phase gamma -Bi2VO5.5 and fluorite-like f-Bi2VO5 not obtained by the traditional solid-state reaction method. Thermal and electrical behavior of these phases has been studied by DTA, XRD with temperature and impedance spectroscopy measurements. Both gamma -Bi2VO5.5 and f-Bi2VO5 transform to well-known alpha -Bi2VO5.5 and alpha -Bi2VO5, respectively, on heating above 500 degreesC. The conductivity and activation energy values of the phases are characteristic of good ionic conductor materials. The sintering protocol seems to be an essential point to improve their electrical properties.