The glasses (80-x)TeO2·xV2O5·20MO (M=Sn, Bi, Ca, Na and K) had been examined as potential replacements for PbO-based glass frits with low firing temperature. The glasses with TeO2 0-44 mol%, and V2O5 39-82 mol% are not suitable for glass frit since they are easy to crystallize. The glasses with the content of the TeO2 54-74 mol%, and the V2O5 9-29 mol% were investigated by differential scanning calorimetry, X-ray diffraction, infrared spectra and fluidity evaluation experiments. The glasses possess appropriate fluidity and do not crystallize in the re-melting process at 723-753 K. The glass transition temperature of the glasses is at 544-578 K. The structure of the glasses is layer upon layer mainly connected by the structure units of [VO4] and [TeO3]. Other modifier ions locate mainly between the layers. The isolated V=O band from the VO5 bipyramids is not occurred in the vitreous structure of the glasses.