Catalytic oxidation of CO, benzene, and toluene was studied over the octahedral layered birnessites (OL-1, OL-2, OL-3, and OL-4) derived from different routes. Physicochemical properties of the samples were characterized by a number of different analytical techniques. It is found that all of the samples have birnessite-type octahedral layered structure and an interlayer spacing of ca. 0.72 nm. Surface areas and pore volumes of the OL-3 and OL-4 samples were much higher than those of the OL-1 and OL-2 samples. There was co-presence of Mn3+, Mn4+ and/or Mn2+ on the surface of these samples. Based on the manganese ion contents, the average oxidation states of surface Mn species in the birnessite samples were in the range of 3.2-3.5, which was lower than those (3.5-3.9) obtained from the H2-TPR studies. The amounts of oxygen vacancies and lattice oxygen mobility of the OL-1 and OL-4 samples were higher than those of the OL-2 and OL-3 samples. Either in CO oxidation or in benzene or toluene oxidation, the catalytic activity decreased in the order of OL-1 > OL-4 OL-3 > OL-2, with the OL-1 sample showing the best performance (T-50% = 115 and T-100% = 150 degrees C for CO oxidation at 15,000 mL/(g h), T50% =200 degrees C and T-95% = 240 degrees C for benzene oxidation, and T-50% =190 degrees C and T-95% =230 degrees C for toluene oxidation at 40,000 mL/(gh)). We conclude that catalytic performance of the octahedral layered birnessite samples was associated with the Mn oxide nature, surface lattice oxygen mobility, and reducibility. (C) 2014 Elsevier B.V. All rights reserved.