The Raman, IR absorption and EXAFS spectra at the Ge K-edge and Pb L III-edge of eight lead germanate glasses, with general formula xPbO(1− x)GeO 2 with x = 0.20, 0.25, 0.33, 0.40, 0.50, 0.53, 0.56 and 0.60, have been measured. The occurrence of [GeO 6] units besides [GeO 4] could not be deduced unambiguously from the data. The vibrational and EXAFS data agree with a progressive depolymerization of the network. Starting from all Ge atoms linked to four bridging oxygens in GeO 2 ( x = 0), the number of tetrahedral units with one or two non-bridging oxygens increases with x. At low content, Pb 2+ ions act as modifiers in the germanate structure, but to a lesser extent than an equivalent number of alkaline ions.