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Heterogeneous interface in materials has recently attracted much attention because of its crucial role in catalytic reaction. Herein, we report the preparation of high-quality Co 3 O 4 -decorated one dimensional (1D) MnO 2 hybrids and their application in catalytic degradation of carcinogenic benzene. Three kinds of 1D MnO 2 including α-MnO 2 nanowires, α-MnO 2 nanorods and β-MnO 2 microrods were firstly synthesized by different hydrothermal method, followed by a controlled Co 3 O 4 functionalized process. The homogeneous coating of the Co 3 O 4 nanoparticles on the surface of the MnO 2 created large amounts of remarkable MnO 2 -Co 3 O 4 heterogeneous interface which was characterized by SEM and TEM techniques. XPS and H 2 -TPR studies revealed the decorated hybrids had better low-temperature reducibility and more active surface adsorbed oxygen species. Compared with the bare MnO 2 , these hybrid MnO 2 @Co 3 O 4 nanaostructures showed improved catalytic reactivity toward gaseous benzene oxidation, and the enhancement had different dependence upon the various MnO 2 . Under high space velocity of 120,000 mL g −1 h −1 , the best-performed α-MnO 2 nanowires@Co 3 O 4 can decrease the T 90 (temperature of 90% benzene conversion) to 247 °C which was almost 100 °C lower than the pure α-MnO 2 nanowires. Their significantly promoted catalytic activity should be attributed to the strong synergistic effect due to the existence of remarkable MnO 2 -Co 3 O 4 hetero-interface. [ABSTRACT FROM AUTHOR]