The molecular structure of the electrical double layer determines the chemistry in all electrochemical processes. Using x-ray absorption spectroscopy (XAS), we probed the structure of water near gold electrodes and its bias dependence. Electron yield XAS detected at the gold electrode revealed that the interfacial water molecules have a different structure from those in the bulk. First principles calculations revealed that ∼50% of the molecules lie flat on the surface with saturated hydrogen bonds and another substantial fraction with broken hydrogen bonds that do not contribute to the XAS spectrum because their core-excited states are delocalized by coupling with the gold substrate. At negative bias, the population of flat-lying molecules with broken hydrogen bonds increases, producing a spectrum similar to that of bulk water.