The effect of oxide dopant on the structure of 62ZrF(4)-30BaF(2)-8LaF(3) (mol%) glass by equimolar substitution of BaO for BaF2 was studied by X-ray photoelectron spectroscopy (XPS). The XPS spectra of La 3d, Ba 3d, F 1s, O 1s and Zr 3d were measured. From the deconvoluted results for the XPS spectra of elements in the glass, it was proposed that the oxide ions added to the glass mainly bond to Zr4+ and replace the bridging fluoride ions resulting in the formation of the F-Zr-O bond. Further analyses indicated that the oxide ions mainly play a non-bridging role instead of a bridging role in the glass structure.