Recent investigations claimed the use of lipscombite, Fe3+2Fe2+(P04)2(0H)2, as a catalyst for the oxidative dehydrogenation of isobutyric acid. In the present study, the synthesis and characterization by Mossbauer spectroscopy of Mn-, Co-, and Cr-substituted lipscombites are described. It is found that lipscombite substituted by lo%, 20%, and 30% of cobalt and manganese could be prepared while the substitution by chromium did not exced 20%. Mossbauer spectroscopy along with other physicochemical characterization techniques showed that [Fe3+2-,M2+,]Fe2+(P04)2-,(HP04),(OH)2 (M = Mn or Co) type solid solutions were obtained instead of Fe3+2[Fe2+~-,M2+,](PO4)2(OH)2 solid solutions which exist for natural compounds. Chromium-substituted compounds belonged to a [Fe3+2-xCr3+,]Fe2+(P04)2(OH)2 limited solid solution ( x 0.3). Mn2+, Co2+, and Cr3+ were found to preferentially occupy in the lipscombite structure two ferric cations sites Fe(3)b and Fe(3)a, which differ by their cationic surrounding.