A facile strategy of redox etching-precipitation is developed to support cerium oxide (CeO_y) on crystal α-type manganese dioxide nanorod (OMS). By means of this method, the contact between CeO_y and OMS can be strengthened and results in enhancement of interfacial effect, thereby causing consequent changes in physicochemical properties. Through screening and evaluation, the as-prepared catalyst of 5.0% CeO_y/OMS (5.0% Ce/OMS) with an optimal Ce/Mn molar ratio of 0.05, owning more acidity, more surficial oxygen vacancies as well as more mobility of lattice oxygen, exhibits a remarkable activity and stability for catalytic oxidation of chlorobenzene. Under catalysis of 5.0% Ce/OMS, the demanded temperature for complete removal of chlorobenzene is about 360 °C, which is lower than the required temperature (above 400 °C) for NH₃-5.0% Ce/OMS prepared via conventional method of NH₃^.H₂O precipitation. Meanwhile, 5.0% Ce/OMS shows a good tolerance to high water content (10 vol.%) and a better recyclability, adapts to oxidation of various kinds of volatile organic compounds (VOCs) and VOCs mixture under simulated realistic exhaust condition. With correlation of structure and performance, it is revealed that interface acts as active site to catalyze oxidation.