Herein, a series of monolithic Mn/Ce-based catalyst of ceramic membranes (CMs) were prepared through impregnation method for volatile organic compounds (VOCs) removal. The porous fibrous CMs with a sinter-locked network structure were fabricated by molding method in a feasible sintering process. Then, the catalytic CMs were systematically analyzed by using specific analytical techniques. The results showed that the fibrous CMs possessed a unique interconnected and uniform pore structure, and MnOx-CeO2 active phases were homogenously dispersed into the porous CMs support. The catalytic activity of samples was measured by using benzene as target VOCs. The results revealed that all catalytic CMs were active for oxidation of benzene. Significantly, the catalytic performance was promoted by introducing Ce species into MnOx. Among all, MnOx-CeO2-3:1 catalyst exhibited the lowest 90% benzene conversion temperature (T-90) at 244 degrees C and high stability with continuous benzene stream in the presence of 90 vol.% (20 degrees C) water vapor under a gaseous hourly space velocity (GHSV) of 5000h(-1), owing to the lower-temperature reducibility and the abundant active oxygen (O-Ads.) with synergetic effect of MnOx and CeO2. The results indicated a promising way to design a high efficiency dual functional CMs for the industrial application of removal VOCs while controlling particulate matters (PMs) from hot gases.