Barium substituted lanthanum manganite perovskite-type oxides were prepared by a liquid precursor method and characterized by X-ray diffraction, oxygen desorption, and X-ray photoelectron spectroscopic studies. XPS analysis revealed the significant changes in the doublet characteristics of the Ols peak (similar to 530 eV) resulting from the substitution of Ba in LaMnO3. A well defined Ba3d spectra was seen only with more than 10 mol% substitution of Ba in La site. Methane oxidation reaction was carried out in a flow reactor with a feed containing 0.28% CH4, 15% oxygen and balance helium. The conversion of methane was followed in the temperature range of 200 to 700 degrees C. The light-off temperature for 50% methane conversion was found to be the lowest (490 degrees C) for La0.9Ba0.1MnO3 composition. Temperature Programmed Desorption (TPD) experiments of oxygen indicate two maxima centered around 320-550 degrees C and 650-760 degrees C respectively. In the low temperature oxygen desorption region, the peak maximum was found to shift with Ba substitution which also corresponded to the activity of methane. The results for oxygen chemisorption and surface composition of these samples are related to the methane oxidation properties.