In this work we report on a vibrational spectroscopic, X-ray diffraction, and density measurement study of the structural properties of the ternary xGd(2)O(3)(100 - x)[7TeO(2)center dot 3V(2)O(5)] systems for various x values up to 70 mol%. Structural changes, as recognized by analyzing band shapes of X-ray diffraction and IR spectra, revealed that Gd2O3 causes a higher extent of network polymerization as far as x <= 40 mol%, while for x between 40 and 50 mol% showed a drastic structural modification which lead to the apparition of the GdVO4 crystalline phase.