In this paper, a density functional theory based on the first-principles was employed to evaluate the adsorption of CH4 onto the surfaces of BaZrO3 catalysts. The absorption mechanism was derived by population and electronic states analysis on the basis of the electronic and surface structure calculations for BaZrO3. The (001) surface was calculated to be the adsorption surface for CH4 owing to its high stability. Comparing to that for CH4 absorbed on (001) surfaces, the frontier energy state was found to the key factor in controlling the adsorption behavior, which is mainly contributed by oxygen and Zr ions of the B-site. The most favorite adsorption site for CH4 was located at B-sites of BaZrO3, where the A-site ions would adjust the charge of B-site ions and moreover affect the CH4 adsorption. The results reported in this work may provide the fundamental understanding about the absorption of CH4 inflammation catalysts with high-activity and high-stability.