The HER activity of a polycrystalline Pt electrode was tested in increasing concentrations of KOH, NaOH, and RbOH (between 0.1 and 6 M). Structural changes in interfacial water were monitored analyzing the OH stretching bands of water and their dependence on the applied bias using SHINERS. Studies on both oxidative (OER) and reductive (HER) potentials are conducted and correlated with the room temperature HER voltammetry/impedance studies.