xCu(2)O . yTeO(2).(1-x-y)MoO3 glasses have been synthesized and characterized by DSC, IR and XPS techniques. Thermal studies have shown that the glass transition temperature (T-g) varies with change in composition from 160 to 310 degrees C. IR studies of the glasses show structural variation of MoO6 octahedral and trigonal bipyramid(tbp)- and trigonal pyramid(tp)-tellurite units with composition change. Through X-ray photoelectron spectroscopy(XPS), the core-levels of Te 3d, Cu 2p, Mo 3d and O 1s electrons were studied. Ionic conductivity was found to be strongly dependent on non-bridging oxygen content estimated from O 1s XPS spectra. Both IR and XPS results have been correlated to provide the structural information.