The local evironments of Cd and Pb cations in the system Cd1−xPbxF2(x = 0.6) have been measured by means of EXAFS. A comparative analysis of the Fourier transforms of the experimental data provides evidence of the Pb-F bond length being longer than the Cd-F one. Furthermore, our studies show a loss of structure around the Pb(L111) edge with increasing temperature. This suggests that the temperature-induced vacancies on the anion sub-lattice are preferentially located adjacent to Pb ions as previously observed in PbSnF4mixed-metal fluorides. The results obtained accord well with our computer simulation findings.