Carbon monoxide is widely known to poison Pt during heterogeneous catalysis owing to its strong donor-acceptor binding ability. Herein, we report a counterintuitive phenomenon of this general paradigm when the size of Pt decreases to an atomic level, namely, the CO-promoting Pt electrocatalysis toward hydrogen evolution reactions (HER). Compared to pristine atomic Pt catalyst, reduction current on a CO-modified catalyst increases significantly. Operando mass spectroscopy and electrochemical analyses demonstrate that the increased current arises due to enhanced H2 evolution, not additional CO reduction. Through structural identification of catalytic sites and computational analysis, we conclude that CO-ligation on the atomic Pt facilitates Hads formation via water dissociation. This counterintuitive effect exemplifies the fully distinct characteristics of atomic Pt catalysts from those of bulk Pt, and offers new insights for tuning the activity of similar classes of catalysts.