A series of manganese oxide octahedral molecular sieve (OMS-2) doped with Co, V, and Ce (Me) with molar ratio Me/Mn = 0.04 and 0.12 were prepared via a one-step reflux method, and were characterized by XRD, SEM, IR, BET, ICP, XPS, and TG techniques. The OMS-2 materials doped with Me having Me/Mn=x are denoted as Me-M(x). It was found that Ce mainly enters the tunnel structure of OMS-2 instead of K, Co mainly substitutes for Mn in the framework, and V is likely to substitution into both the Mn and K in the cryptomelane tunnel structure. The length of OMS-2 rods decreases with the decline of K+ mole fraction in the OMS-2 tunnels. Doping V and Ce markedly decreases the crystallization of OMS-2. Ce-M(0.12) shows a specific surface area (142 m(2) g(-1)) roughly double that of OMS-2 (69 m(2) g(-1)). All the Me-M(x) materials were tested as catalysts for the oxidation of p-chlorotoluene to p-chlorobenzaldehyde with molecular oxygen, and it is Ce-M(0.12) that shows the highest catalytic activity. The excellent performance is attributed to the large specific surface area and good mobility of oxygen species of the Ce-M(0.12) material. (C) 2016 Elsevier B.V. All rights reserved.