The thermal decomposition of sodium hexa-carboxylato/ferrates/III/ i.e. Na3[Fe/RCOO/6].xH2O /R=H, CH3, C2H5/ has been studied at various temperatures in air employing Mössbauer and infrared spectroscopies and non-isothermal techniques /DTG, DTA, TG/. The thermolysis proceeds without undergoing the formation of any iron/II/ intermediate. The particle size of α-Fe2O3 formed during thermolysis shows an increasing trend with increasing decomposition temperature. At higher temperatures α-NaFeO2 is formed as the ultimate product for all the complexes.