The Fischer-Tropsch reaction is initiated by direct CO dissociation for Iron catalyst even though a H-assisted mechanism may be easier on other metals. In the gas phase, the CO dissociation is only favorable for Fe-clusters composed by more than 11 atoms. We show here the remarkable effect of the support TiO2(1 1 0), making this dissociation exothermic for Fe-4 and Fe-5 clusters. The main factor for the CO activation is the electron transfer to the reducible support. The role of the TiO2(1 1 0) support is to transform the neutral cluster into a positively charged one for which CO dissociation is easier. (C) 2017 Elsevier B.V. All rights reserved.