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Neutron and x-ray diffraction experiments of high resolving power with neutrons from a spallation source and high-energy photons from a synchrotron have been performed on compositional series of binary Zn, Nb and on mixed Zn/Nb tellurite glasses. The Te-O, Zn-O and Nb-O coordination numbers are determined by Gaussian fitting of the first-neighbour peaks in the neutron and x-ray data simultaneously. The transition of TeO 4 to TeO 3 units with increasing fraction of a second component is indicated by decreasing total Te-O coordination numbers. This transition appears different for glasses with ZnO or Nb 2 O 5 additions. Details of the Te-O peaks suggest there are two species of Te-O bonds with lengths of ∼0.19 and ∼0.21 nm. The change of their fractions shows excellent agreement with the existence of TeO 4 trigonal bipyramids and TeO 3 trigonal pyramids. All oxygen atoms from ZnO and Nb 2 O 5 are used for rupture of Te-O-Te bridges, which is accompanied with a change of nearly all participating TeO 4 to TeO 3 groups. The tendency for a TeO 4 → TeO 3 change decreases for glasses of higher second component content which is accompanied by the occurrence of TeO 4 groups with non-bridging oxygens. The Nb tellurite glasses show transition to network-forming behaviour with the formation of Nb-O-Nb bridges. The fractions of TeO 3 units of ternary Zn/Nb tellurite glasses agree with an additivity behaviour of the modifying effects of ZnO and Nb 2 O 5 additions. * Some of these results have already been presented in thesis work: Yousef E 2003 A study of some physical properties of tellurite glass (Al-