xFe 2 O 3 ·(100−x)[Bi 2 O 3 ·CdO] system with 0≤x≤50mol% was prepared and investigated by X-ray diffraction, density, FT-IR and Raman spectroscopies. The XRD patterns confirm the formation of a vitreous structure for x<35mol% Fe 2 O 3 . The evolution of density and molar volume with the addition and increasing of iron content indicates structural changes in the structure of Bi 2 O 3 ·CdO glass matrix. The FT-IR spectrum of the glass matrix reveals a structure realized from BiO 3 pyramidal and BiO 6 octahedral units. With the addition of iron the structure proposed by the glass matrix is changing by the appearance of FeO 4 units. Also the existence of FeO 6 units cannot be excluded. The Raman spectra suggest a structure build from BiO 6 octahedral units. By Raman scattering the presence of structural units characteristic to Fe 2 O 3 was not directly observed but the evolution of the spectra is dependent of the iron content.