Three-dimensionally ordered macroporous (3DOM) LaFeO3 and nano-LaFeO3 perovskitetype oxides were synthesized by impregnation of polystyrene (PS) templates and combustion method, respectively. The obtained LaFeO3 perovskites were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), Brunauer Emmett Teller (BET) surface area, and hydrogen-temperature programmed reduction (H-2-TPR). The performance of the perovsldtes as oxygen carriers in chemical looping steam methane reforming (CL-SMR) to produce syngas (H-2 + CO) and hydrogen were investigated. The synthesized 3DOM-LaFeO3 was pure crystalline perovskite giving a surface area of 8.088 m(2)/g, higher than that of nano-LaFeO3 particles (4.323 m(2)/g). In the methane reduction stage, methane was partially oxidized into syngas at a H-2/CO molar ratio close to 2:1 by the 3DOM-LaFeO3 in the main stage of the reactions. In the steam oxidation stage, the reduced perovskites were oxidized by steam to generate hydrogen simultaneously. No significant decrease of the yields of syngas and hydrogen was observed during ten successive redox cycles, indicating that the 3DOM-LaFeO3 perovskites have good repeatability. In comparison to nano-LaFeO3, 3DOM-LaFeO3 has more stable reactivity of methane oxidation and better resistance to carbon formation. In spite of a part of 3DOM structure were collapsed in the course of the cyclic reactions, the specific surface area of the 3DOMLaFeO(3) was still higher than that of the nano one. The better reactivity of 3DOM-LaFeO3 compared with that of nano-LaFeO3 is partially attributed to the higher surface area. Copyright (C) 2013, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.