CuNi bimetallic alloy particles supported on CeO2 are prepared by coprecipitation of the corresponding salt precursors followed by calcination and hydrogen reduction. The supported alloy particles are characterized by PXRD, H2-TPR, XPS, XANES and EXAFS techniques. The PXRD study shows that copper rich oxide phases supported on CeO2 are reduced at 200 °C. However, complete reduction of CuO-NiO phases occurs at 450 °C forming CuNi alloy particles on CeO2. The H2-TPR results show that mixed oxides are reduced at higher temperatures than pure components indicating strong wetting between oxide components and CeO2. The Ni 2p XPS shows stronger interaction between Ni2+ and CeO2 support. XANES and EXAFS studies show the formation of CuNi alloy particles with small surface segregation of Cu. The catalytic activity of the supported CuNi alloy particles is studied by non-oxidative dehydrogenation of cyclohexanol to cyclohexanone reaction. The effect of temperature, contact time and time on stream are examined to gain insights into the catalytic activity of the CeO2 supported CuNi alloy catalysts. Among all the CuNi alloy compositions, CuNi(1:1)/CeO2 catalyst shows higher catalytic activity and selectivity to cyclohexanone. Formation of stable CuNi alloy particles on CeO2 by alloy-redox support interaction and segregation of Cu are crucial factors for catalytic activity. © 2012 Elsevier B.V.