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The structures of V2 O5 -TeO2 glasses are investigated by means of 125 Te and 51 V static NMR spectroscopies and the local structures around the Te and V atoms are discussed in detail from the respective NMR spectra. The fraction of TeO3 trigonal pyramids increases and that of TeO4 trigonal bipyramids decreases with increasing V2 O5 content. The structures of V2 O5 -TeO2 glasses are quite different from those of tellurite glasses containing network-modifying oxides. The fraction of VO4 tetrahedra increases and that of VO5 trigonal bipyramids decreases with increasing V2 O5 content. Both chains consisting of tellurite structural units and those consisting of vanadate structural units contribute to the formation of the glass network in V2 O5 -TeO2 glasses.