In this paper, we have examined and analyzed the effects of systematic intercalation of the lead ions on vanadate-tellurate glass ceramics with interesting results. The structural properties of the lead-vanadate-tellurate glass ceramics of compositions xPbO center dot(100 - x)[6TeO(2)center dot 4V(2)O(5)], x = 0 - 100 mol%, are reported for the first time. It has been shown by X-ray diffraction that single-phase homogeneous glasses with a random network structure can be obtained in this system. Among these unconventional lead-vanadate-tellurate glass ceramics, we found that network formers are good host material for lead ions and are capable to intercalate a variety of species such as Te2V2 O-5+(9), Pb-3(V5+O4)(2), Pb2V2 O-5+(7), and V2O5-rich amorphous phase. On the other hand, these glass ceramics contain V4+ and V5+ ions necessary for the electrical conduction. Based on these experimental results, we propose that the V4+=O bonds are created by two different mechanisms: the first of reduction of V5+ ions to V4+ ions and thus of creation of V4+=O bonds.