The hydrogenation reaction of carbon dioxide and a mixture of carbon oxides on bimetallic catalytic systems containing nanoparticles of Fe, Ni, Co, and Mn supported on an inert carrier is studied. It is found that the ratio of saturated and unsaturated hydrocarbons in the hydrogenation products and the synergistic effect are determined mainly by the number of hydrogen atoms that are capable of migrating from one active center to another and by composition of those centers. Differences in the catalytic activity and selectivity of the bimetallic samples are explained by different rates of the spillover of weakly bound hydrogen (H I) and the different rates of the jumpover of CH x radicals from one center to another at which their further hydrogenation takes place. © 2012 Pleiades Publishing, Ltd.