We use second harmonic generation spectroscopy, molecular dynamics simulation, and theoretical modeling to study the response of the neat liquid water-air interface to changes in the potential of an external electrode positioned above the liquid. We observe a parabolic dependence of second harmonic intensity on applied potential, indicating that water’s net interfacial dipole responds linearly. We also observe a minimum intensity when the potential is tuned to a specific positive value. Interpreting this minimum based on the macroscopic electrostatic potential profile yields misleading physical conclusions because it neglects the internal bias exerted on molecular orientations by the excess surface concentrations of OH- or H3O+. We thus find that water’s net interfacial dipole orientation is primarily responsive to the effects of these ionic species rather than the external electric field.