Two kinds of amorphous Li+ conductor, B2O3-0.7Li2O-0.7LiCl-xAl2O3-0.1V2O5(x= 0.05 and 0.15), were studied with differential thermal analysis, conductivity measurement, X-ray diffraction and ESR spectroscopy. We find that: (1)V2O5 not only is amorphous network former, but also changes the process of crystallization;(2) For both the B2O3-Li2O-LiCl-Al2O3-V2O5 glasses and the P2O5-Li2O-LiCl-Al2O3 glasses,ionic conductivity of the tablet sample is 26 times higher than that of 60 mesh powder sample of the same material; the whole piece of glass has an obviously lower activation energy and a conductivity that is two orders higher than that of the tablet sample, so it is more suitable for ion transport; (3) Adding V2O5 less than 3.9mol% to amorphous Li+ conductor B2O3-0.7Li2O-0.7LiCl-xAl2O3(0≤x≤0.15) does not cause electron-conductivity to increase rapidly. Further more, this makes it possible to apply the technique of ESR to study the micro structure of and electron movement in the material.