The study investigates the effect of ion-specific water structures on hydrogen production at metal surfaces. Using scanning tunneling microscopy (STM) and noncontact atomic force microscopy (AFM), the researchers visualized water layers containing alkali metal cations (Li⁺, K⁺, and Cs⁺) on a charged Au(III) surface with atomic resolution. The results show that Li⁺ cations are elevated from the surface, forming an ice-like water layer between them and the surface, while K⁺ and Cs⁺ cations are in direct contact with the surface. The water network structure transitions from a hexagonal arrangement with Li⁺ to a distorted hydrogen-bonding configuration with Cs⁺. These findings are consistent with surface-enhanced infrared absorption spectroscopy (SEIRAS) data and suggest that alkali metal cations significantly impact the kinetics and efficiency of the hydrogen evolution reaction (HER). The study provides insights into ion-specific water structures on metal surfaces and highlights the critical role of spectator ions in electrochemical processes.The study investigates the effect of ion-specific water structures on hydrogen production at metal surfaces. Using scanning tunneling microscopy (STM) and noncontact atomic force microscopy (AFM), the researchers visualized water layers containing alkali metal cations (Li⁺, K⁺, and Cs⁺) on a charged Au(III) surface with atomic resolution. The results show that Li⁺ cations are elevated from the surface, forming an ice-like water layer between them and the surface, while K⁺ and Cs⁺ cations are in direct contact with the surface. The water network structure transitions from a hexagonal arrangement with Li⁺ to a distorted hydrogen-bonding configuration with Cs⁺. These findings are consistent with surface-enhanced infrared absorption spectroscopy (SEIRAS) data and suggest that alkali metal cations significantly impact the kinetics and efficiency of the hydrogen evolution reaction (HER). The study provides insights into ion-specific water structures on metal surfaces and highlights the critical role of spectator ions in electrochemical processes.