Magnetic susceptibility and XPS results on x Fe 2O3 · (100-x) [4 Bi 2O3 · PbO] where 0<x ≤20 samples are presented in order to point out the oxidation states and the distribution of iron ions in the lead-bismuthate matrix. The valence state of iron ions changes from Fe3+ to Fe2+ as the Fe2O3 content increases from 1 to 20 mol%. The XPS data indicate the migration of metallic elements in the inner part of the bulk investigated samples.