Silver selectively catalyzes the hydrogenation of the CO group of α,β-unsaturated aldehydes, indicating preferential adsorption-induced activation of this bond compared to the adjacent CC bond. Using a density functional method and periodic slab models, we studied the propensity of the flat Ag(110) and the stepped Ag(221) surfaces to activate the CO bond of adsorbed acrolein. Our calculations show acrolein to interact only weakly with all adsorption sites under study (by at most 35kJmol −1 ), resulting in very limited bond activation. Therefore, we conclude that other active sites on silver catalysts participate in the experimentally observed selective hydrogenation.