In the present work, cerium iron phosphate glasses were studied to examine the effect of the CeO2 composition on the structure of the iron phosphate glasses system. Cerium iron phosphate samples with the compositions, I: xCeO(2)-(40 - x)Fe2O3-60P(2)O(5) and H: xCeO(2) (100 - x)(40Fe(2)O(3)-60P(2)O(5)) (x = 030 mol%) have been prepared. The structure of glasses has been studied using X-ray diffraction (XRD), Raman spectrum, Fourier transform infrared spectrum (FT-IR) and differential thermal analysis (DTA), especially focusing on the structure dependence on the CeO2 content. The glass formation occurs at series at series II, the crystalline phases are detected in the samples. The Q(1) groups are the predominant structural units in glasses with the cerium-free and 10 mol% CeO2 content. With increasing CeO2 content in glass compositions, the P-O-P network get extensively depolymerised, resulting in the systematic conversion of Q(1) to Q(2) structural units. The Q units can be detected in the all glasses compositions. The glass transition temperature (TO linearly increase with the addition of CeO2 content, indicating an increase in thermal stability tendency with increasing CeO2 content. The change of T, is consistent with structural modification of glass. (C) 2011 Elsevier B.V. All rights reserved.