Barbosalite and lipscombite hydroxyphosphates have been prepared and characterized by Mössbauer spectroscopy. These phases have been shown to be constituted of chains of Fe—oxygen octahedra sharing faces. The principal difference in the arrangement of the ions in these structures is the organization of the octahedra in the chains. In barbosalite, the chains are composed only of trimeric groups (Fe₃O₁₂) separated by a vacant octahedral site, while lipscombite chains are composed of groups of (2n + 1) iron cations,n varying from 0 to 5 or 6. The relative abundance of the different groups was calculated from published X-ray diffraction data and used to attribute the three ferric and the two ferrous doublets observed in the Mössbauer spectrum of lipscombite. This attribution is confirmed by the comparison with the results obtained on barbosalite.