We have used vibrational sum frequency generation spectroscopy to study the water structure at the interface of carbonate electrolyte solutions and a gold electrode under applied potentials relevant to CO 2 R. We observed a peak at around 3400 cm -1 at catalytic potentials in the presence of carbonate anions, and this peak is assigned to a sodium-carbonate ion complex, which is over-represented near the interface. The peak is much more prominent for Na 2 CO 3 than Cs 2 CO 3 suggesting this peak is not only anion specific but also cation specific. Using molecular dynamics simulations, we link these observed spectral changes to the impact of carbonate on the potential-dependent alignment of interfacial water and the creation of a solvent separated sodium-carbonate ion pair. The peak around 3400 cm -1 is assigned to water molecules in the first solvation shell of a CO 3 2anion near the interface, which show a preferential orientation of their OH bonds. This orientation disrupts the inversion symmetry, leading to the visibility of their vibrations in the VSFG spectrum. The solvent-separated configuration of the ion pair shows markedly different behavior from the contact ion complex. Instead of a bistable conformation, the solventseparated ion pairs displays a broad range of angular displacements with a sharp peak in a highly bent configuration with the two sodium ions separated from one another by one water molecule. This solvent-separated bent configuration is found in all chemical environments but is significantly enhanced near electrode surface. These findings reveal ion pairing plays an important role in the structure alignment of interfacial water under conditions relevant for electrochemical catalysis, including CO 2 R and lays the groundwork for future studies to further consider the impact of these structures on the kinetics and mechanisms of electrochemical reactions.