Résumé : We studied the interplay between Ag decoration of a stepped Pt(355) surface and CO adsorption by in situ high-resolution x-ray photoelectron spectroscopy. Varying amounts of Ag deposited at 300 K initially lead to a row-by-row growth starting from the lower Pt step edges. Such decoration of the step sites results in a change in the CO adsorption behavior. An apparent blocking of step sites for low CO coverages is attributed to a change in the electronic structure, resulting in a C 1s binding energy of CO at step sites being equal to that for CO at terrace on-top sites in the presence of Ag. Higher CO coverages induce the formation of embedded Ag clusters within the upper terraces, thus freeing up a part of the original Pt step sites for CO adsorption, as was derived by a comparison to density functional theory calculations in the corresponding surface models.