Thermal decomposition of the coordination polymer, (NH4)La[Fe-II(CN)(6)]center dot 4.5H(2)O, with a three-dimensional network structure formed by the Fe-II-CN-La-III linkages, was investigated. The decomposition began at around 323 K and proceeded via a few steps to give the anhydride complex, (NH4)La[Fe-II(CN)(6)], at around 523 K. Further heating gave rise to an abrupt collapse of cyanide groups at around 573 K, followed by the initial formation of the perovskite-type oxide, LaFeO3, at 603 K and the completion of the decomposition to produce LaFeO3 at around 898 K. Any formation of the component metal oxides, La2O3 and Fe2O3, was not recognized during the decomposition. From the XRD line broadening using Scherrer's equation, the average size of the thermal decomposition product was evaluated to be 21, 22, 25 and 30 nm at 773, 823, 898 and 1073 K, respectively. The specific surface area of the LaFeO3 particles prepared at 898, 1073 and 1273 K was 13.2, 8.6 and 2.5 m(2) g(-1), respectively. (C) 2010 The Ceramic Society of Japan. All rights reserved