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Details of the Te-O first-neighbor distances in V 2 O 5 -TeO 2 glasses were obtained by neutron diffraction experiments with a measuring range up to Q max =400nm -1 (Q is the magnitude of scattering vector). A sharp Te-O peak at 0.191nm and a second broad component at about 0.21nm were resolved. Quantitative analyses of the areas of both peak components for a compositional series of four samples support the model of a change of TeO 4 trigonal bipyramids to TeO 3 trigonal pyramids upon V 2 O 5 additions. In glasses of up to ~10mol% V 2 O 5 each VO n polyhedron introduced is accompanied by the formation of a TeO 3 unit. The number of TeO 3 units increases further for glasses of higher V 2 O 5 concentrations but the increase is less than that of the number of V sites.