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.