Vicinal surfaces are important in surface science, as they show interesting electronic structures and reactivities due to the steps. In this paper the adsorption and desorption of carbon monoxide on the stepped Rh(553) surface decorated with Ni is reported. With 0.1 to 0.3 monolayer Ni on Rh(553) one and two atoms broad Ni wires along the Rh steps are formed. The adsorption and desorption of carbon monoxide on these surfaces is investigated using thermal desorption spectroscopy (TDS) and reflection absorption infra red spectroscopy (RAIRS). TDS shows a marked change from just one broad TDS peak on pure Rh(553) to 4 distinct peaks with increasing Ni decoration. RAIRS shows that already at 0.1 monolayer Ni the CO adsorption states on bridge sites on the Rh step atoms are completely quenched. In addition it is shown that with Ni films up to 3 monolayer the on top adsorption sites for CO on Ni are preferred over the bridge and hollow adsorption sites in contrast to what is known from the Ni(111) surface.