Glasses in the system xGd(2)O(3)center dot(100 - x)[TeO2 center dot GeO2] with 0 a parts per thousand currency sign x a parts per thousand currency sign 50 mol% have been prepared from melt quenching method. In this paper, we investigated changes of the coordination numbers of germanium, tellurium, and gadolinium ions by investigations of FTIR, EPR, and UV-VIS spectroscopy. By analyzing the structural changes resulted from the IR spectra we found that the bending modes of [GeO4] structural units and the deformed modes of the Te-O-Te linkages produce intercalation of the [GdO (n) ] entities in the germanate-tellurate chain network and densification of the glasses by increasing the number of [GeO6] structural units. EPR spectra of the studied samples reveal that the gadolinium ions play a role of network former. The UV-VIS spectra show broad UV absorption bands located in the 250-350 nm region. Their intensity increase with the increasing of Gd2O3 content showing that these stronger transitions can be due to the presence of the O=Ge bonds (n-pi* excitations) of [GeO5] structural units. The [GeO5] structural units are more stable thermodynamically than their analogues and the [GeO6] structural units produce the improvement of the amorphous character of these glasses.