Water interfaces provide the platform for many important biological, chemical, and physical processes. The water–air interface is the most common and simple aqueous interface and serves as a model system for water at a hydrophobic surface. Unveiling the microscopic (<1 nm) structure and dynamics of interfacial water at the water–vapor interface is essential for understanding the processes occurring on the water surface. At the water interface the network of very strong intermolecular interactions, hydrogen‐bonds, is interrupted and the density of water is reduced. A central question regarding water at interfaces is the extent to which the structure and dynamics of water molecules are influenced by the interruption of the hydrogen‐bonded network and thus differ from those of bulk water. Herein, we discuss recent advances in the study of interfacial water at the water–air interface using laser‐based surface‐specific vibrational spectroscopy. Lightly scratching the surface: A central question regarding the water–air interface is to what extent the structure and dynamics of water molecules is influenced by the breaking of hydrogen bonds, and thus how they differ from those in the bulk water? One method to study the water–air interface is the laser‐based surface‐specific vibrational spectroscopy. The advances made by these investigations are presented and discussed.