La1-xCaxFeO3 (X = 0.1, 0.2, 0.3, 0.4, 0.5) perovskites prepared by citrate method and calcined at 1073 K have been investigated as catalysts for methane combustion. The formation of the perovskite structure has been shown by X-ray diffraction (XRD) for all samples. The surface area (SA) values are in the range 3-6 m(2) g(-1) for the samples up to x=0.4, whereas SA is 0.7 m(2) g(-1) for the specimen with x = 0.5. The atomic susceptibility increases with increasing in Ca content. The Fe4+/Fe-total ratio has been determined by both redox titration and TPR analysis. The amount of Fe4+ enhances with Ca substitution but the Fe4+/Ca2+ ratio is quite constant giving rise to an increasing formation of oxygen vacancies to preserve charge neutrality. All perovskites show a similar intrinsic activity in CH4 combustion with activation energy, E-a, of about 23 kcal mol(-1). A slightly lower value of E-a is shown by LaFeO3 which, in contrast with Ca substituted samples, exhibits a small cationic defectivity. Methane reaction order lower than one was found for all catalysts.