Supported nickel catalysts are studied for the liquid phase C-C self-coupling of aliphatic secondary alcohols under additive free conditions in N-2 atmosphere. Among various Ni catalysts, 1 or 3 wt% Ni/CeO2 catalysts pre-reduced in H-2 shows highest yield (94%) of a dimer product (a higher ketone) for the self-coupling of 1-octanol at 130 degrees C, and the catalyst is reused. The catalysts are also effective for self-coupling of various secondary alcohols, providing the first heterogeneous catalytic system for the self-coupling of secondary alcohols under mild conditions. Effects of support material and oxidation state of Ni on the activity are studied and it is found that both CeO2 and metallic Ni are indispensable for the reaction. A possible reaction mechanism is proposed, in which ketones, formed by dehydrogenation of alcohol, undergone Aldol condensation to give alpha,beta-unsaturated ketone which is finally hydrogenated by in situ formed Ni-H species. (C) 2013 Elsevier B.V. All rights reserved.