Fast-anion-conducting glasses in the system xPbF₂:(1-x)B₂O₃ have been synthesized and analysed by thermal, electrical and spectroscopic techniques. The ionic conductivity ( sigma ) of these glasses is measured as a function of temperature and chemical composition by the complex impedance method and the results indicate that the conduction of fluorine as charge carriers is governed by activation energy alone. Infrared and X-ray photoelectron spectroscopy studies have provided evidence for fluorine participation in the berate network. Further, the compositional dependence of X-ray photoelectron F 1s spectra indicates that fluorine is incorporated predominantly as B-O-F and Pb-O-F bonds in the oxide network at high B₂O₃ and PbF₂ content respectively. The spectroscopic results obtained are discussed in relation to anionic conduction.