The Cu,Cr-, Zn,Cr- and Cu,Al-layered double hydroxides have been synthesized by the coprecipitation method and characterized by elemental analysis, PXRD, SEM/EDS and BET. The mixed oxide materials obtained upon calcination at 873 K show very high catalytic activity for the combustion of toluene and ethanol. The best sample is derived from the Cu,Cr-LDH precursor with a Cu:Cr ratio of 2, composed of copper oxide and copper chromite. This catalyst gave 50% conversion of toluene and ethanol at temperatures of 45 and 15 K lower, respectively, than the reference commercial catalyst. Catalytic tests with a mechanical mixture of CuO and CuCr2O4 demonstrate that the use of an LDH precursor is essential for optimum results. The importance of the simultaneous presence of both Cu and Cr, the influence of the Cu:Cr ratio on the catalytic activity and the role of the interface boundaries in the CuO-CuCr2O4 mixed oxide system are discussed.