The exceptional properties of liquid water such as thermodynamic, physical, and dielectric anomalies originate mostly from the hydrogen-bond networks of water molecules. The structural and dynamic properties of the hydrogen-bond networks have a significant impact on many biological and chemical processes in aqueous systems. In particular, the properties of interfacial water molecules with termination of the network at a solid surface are crucial to understanding the role of water in heterogeneous reactions. However, direct monitoring of the dynamics of hydrogen-bonded interfacial water molecules has been limited because of the lack of a suitable surface-selective spectroscopic means in the terahertz (THz) frequency range where collective vibrations of water exist. Here we show that hydrogen-bond vibrations below 9 THz can be measuredin situat an electrochemical interface, which is buried between two THz-opaque media, by using a density of states format of surface-enhanced inelastic light scattering spectra. The interpretation of the obtained spectra over the range 0.3–6 THz indicates that the negatively charged surface accelerates collective translational motions of water molecules in the lateral direction with the increase of hydrogen-bond defects. Alternatively, the positively charged surface results in suppression of lateral mobility. This work gives a new perspective onin situspectroscopic investigations in heterogeneous reactions.