A series of three-dimensionally ordered macro-mesoporous (3DOMM) La1-xCaxFeO3 (x = 0-0.3) perovskite-type oxides were designed and successfully fabricated for the first time via a dual-template method. In which, PMMA and Brij-56 were employed as the hard template and soft template, respec-tively. It is found that 3DOMM La1-xCaxFeO3 exhibits abundant wormlike mesoporous channels about 3 nm in diameter on macroporous skeleton walls. The excellent catalytic activity of soot combustion benefits from not only the well-designed hierarchical porous structure of catalyst, but also the redox electron pair of Fe3+/Fe4+induced by the doping of low-valent alkaline earth metal Ca to A-site of LaFeO3. 3DOMM La0.8Ca0.2FeO3 exhibits superior catalytic performance for soot combustion, which shows T50 of 396 ℃. It is 189 ℃ lower than that without catalyst. A combination of structure and composition in the design of catalyst can be widely extended to other catalytic systems.