In the present computational study, we investigate the competitive reaction pathways for the conversion of syngas to the formation of C-1 and C-2 oxygenated compounds such as formaldehyde, methanol, acetic acid. acetaldehyde and ethanol on a Rh-6 cluster. Moreover we also present pathways for the formation of methane and water, which are considered to be the major by-products in the syngas conversion. Our results demonstrate that the formation of the C-1 oxygenates takes place via the hydrogenation of the adsorbed CO molecule while the formation of C-2 oxygenates proceeds in two steps, i.e. CO dissociation to produce CHx, species followed by CO and/or HCO insertion. An analysis obtained from the present calculations reveals that the product formation on Rh-6 cluster depends upon the CO:H-2 coverage. Under hydrogen rich conditions, the products will mainly consist of CH3OH, CH4 and water. The kinetic analysis based on rate constants obtained from harmonic transition state theory indicates that the initial step of CO hydrogenation is the rate-limiting step. Moreover, results suggest that the CO dissociation and the insertion steps for the formation of C-2 oxygenates on Rh-6 cluster have lower barriers compared to that on the Rh(1 1 1) surface. (C) 2010 Elsevier B.V. All rights reserved.