Perovskite LaFeO3 and derived materials La(1-epsilon)FeO(3-1.5epsilon) with epsilon = 0. 1, 0.2, 0.3 have been prepared as polycrystalline powders by thermal low-temperature decomposition of La and Fe nitrates, a method which ensures a high surface area. They have been used in catalytic methane combustion in the range 300-450 degreesC, showing a 100% selectivity to carbon dioxide. The reaction is indeed characterised by two ranges with different dependence of the reaction rate on temperature, as shown by the Arrhenius plot, whose slope decreases markedly above about 375 degreesC. Temperature programmed desorption experiments of oxygen allowed us to ascertain the presence of two surface oxygen species, whose desorption occurs, respectively before and after the above indicated temperature on this basis, we propose here an hypothesis on the way of working of the catalysts. The characterisation of the catalysts has been then completed by means of temperature programmed reduction, whose results contribute to strengthen the hypothesis that the catalyst reduction operated by methane involves a smaller number of lattice planes than reduction of hydrogen. (C) 2002 Elsevier Science B.V. All rights reserved.