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Water is an integral component in electrochemistry, in the generation of the electric double layer, and in the propagation of the interfacial electric fields into the solution; however, probing the molecular-level structure of interfacial water near functioning electrode surfaces remains challenging. Due to the surface-specificity, sum-frequency-generation (SFG) spectroscopy offers an opportunity to investigate the structure of water near working electrochemical interfaces but probing the hydrogen-bonded structure of water at this buried electrode–electrolyte interface was thought to be impossible. Propagating the laser beams through the solvent leads to a large attenuation of the infrared light due to the absorption of water, and interrogating the interface by sending the laser beams through the electrode normally obscures the SFG spectra due to the large nonlinear response of conduction band electrons. Here, we show …