Reactions in aqueous-alcoholic solution between diphenyl-4-amine barium sulphonate (Ba-DAS—anionic surfactant) and the hydrated sulphates of Fe(III) and Fe(II) ions and their use to ovtain iron oxides are described here. The formation of Fe(II) complexes was reached by using an excess of Ba-DAS, in absence of light under inert atmosphere. The complexes achieved Fe2[(C12H10NO3S)4]·9H2O and Fe3[(C12H10NO3S)6]·12H2O were characterized by TG/DTG and IR, UV-VIS and 57Fe-Mössbauer analyses.