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Abstract: Alkyne hydrogenation, a widely used process in industry to purify olefin streams, comprises a prototype reaction to understand selectivity in heterogeneously catalyzed reactions. The selectivity of the reaction on palladium catalysts to the alkene, alkane, or oligomers strongly depends on the state of the (sub)surface; i.e., the occurrence of complex carbide/hydride phases. In practice, hydrogenation reactors in C2 and C3 cuts of steam crackers require continuous CO feeding in order to enhance the alkene selectivity of palladium-supported catalysts. In the present work, we have studied the impact of carbon monoxide on the formation of carbide and hydride phases as a standpoint to derive structure–performance relationships under realistic process conditions. For this purpose, catalytic tests on a standard 1wt.% Pd/Al2O3 and Density Functional Theory on Pd(111) were combined. The influence of: (i) the alkyne (ethyne and propyne), (ii) the hydrogen:alkyne ratio (1–10), (iii) the carbon monoxide:hydrogen ratio (0–0.2), and (iv) the catalyst pretreatment on the product distribution was assessed in a continuous flow fixed-bed reactor at ambient pressure. In absence of CO, subtle changes in the hydrogen:alkyne ratio generate undesired products. Carbon monoxide enables the external control of the catalyst state by suppressing the formation of subsurface hydride and carbide phases, thereby stabilizing a high alkene yield in a broad range of feed hydrogen:alkyne ratios. This scenario contrasts with the more fragile regime of the hydride–carbide phases under CO-free conditions. DFT calculations obtained a single Brønsted–Evans–Polanyi relationship independently of the state of the catalyst (carbide, hydride, CO-covered) and the alkyne–alkene–alkane set (C2, C3). [Copyright &y& Elsevier]