Porous and dispersed CuCo-based mixed metal oxides catalysts (denoted as CuxCo3-xAl-MMO) are obtained via the calcination of ternary CuxCo3-xAl-layered double hydroxide (LDH) precursors, which exhibit excellent catalytic activity towards complete oxidation of benzene. The Cu0.5Co2,5Al-MMO sample shows the maximum activity of 2.41 mmol g(cat)(-1) h(-1) with 90% benzene conversion at 290 degrees C at a high space velocity (SV=60,000 mLg(-1) h(-1)), comparable to that of only 8% conversion for Cu3Al-MMO sample. The significantly enhanced activity is correlated with higher surface area, narrower pore size, low-temperature reducibility and rich oxygen vacancies and lattice oxygen derived from the synergistic effect over porous and dispersive CuxCo3-xAl-MMO catalysts containing CuO and Co3O4 spinel mixed oxides verified by XRD, BET, H-2-TPR, TEM and XPS measurements. Stability with prolonged time on benzene stream and the resistance to water vapor are further investigated. In addition, a monolithic CuCoAl-MMO film catalyst is fabricated by an in situ growth-calcination method, which displays comparable catalytic activity with CuxCo3-xAl-MMO powder. Therefore, this work provides a facile method for the preparation of CuCo-based catalysts with excellent characters responsible for better catalytic activities, which can be used as promising candidates for practical VOCs oxidation. (C) 2014 Elsevier B.V. All rights reserved.