Thermolysis of cesium hexa(carboxylato)ferrate(III) precursors, Cs3[Fe(L)6].xH2O (L = formate, acetate, propionate, butyrate), has been carried out in flowing air atmosphere from ambient temperature to 1000°C. Various physico-chemical techniques, that is, simultaneous TG-DTG-DTA, XRD, TEM, IR, Mössbauer spectroscopy, have been employed to characterize the intermediates and end products. After dehydration, the anhydrous precursors undergo exothermic decomposition to yield various intermediates, that is, cesium carbonate/propionate/butyrate and α-Fe2O3. A subsequent decomposition of these intermediates leads to the formation of cesium ferrite above 800°C. Similar ferrite has been prepared by the combustion method at comparatively lower temperature (600°C) and in less time than that of conventional ceramic method.