The thermal decompositions of sodium ferricarboxylates containing uni-, bi- and tridentate ligands, namely formate, oxalate and citrate, were studied up to 1073 K in static air atmosphere employing Mossbauer and infrared spectroscopic techniques, and nonisothermal methods (TG, DTA, DTG). Except for the citrate complex, the thermolysis proceeds without the formation of any iron(II) intermediate. The particle size of the alpha-Fe2O3 formed during the decomposition increases with increasing decomposition temperature. Finally, a solid state reaction between alpha-Fe2O3 and sodium carbonate/oxide occurs leading to the formation of fine particles of alpha-NaFeO2.