The electrochemical characteristics of two distinct adsorption sites of H at the polycrystalline Pt/0.2 M LiOH aqueous electrolyte interface have been studied using the phase-shift method. At the forward and backward scans, the under-potentially deposited H (WD H) peak occurs on the cyclic voltammogram. The transition region on the phase-shift profile or the Langmuir adsorption isotherm occurs at ca. -0.66 to -0.96 V vs. SCE. At the transition region (ca. -0.66 to -0.96 V vs. SCE), the equilibrium constant (K) for H adsorption transits from 18.5 to $4.0 imes10^{-5}$ and vice versa. Similarly, the standard free energy $({Delta}G_{ads})$ of H adsorption transits from -7.2 to 25.1kJ/mol and vice versa. The under and over-potentially deposited H (UPD H and OPD H) on the poly-Pt surface act as two distinguishable electroadsorbed H species. An exothermic reaction occurs at the UPD H range. Both the UPD H peak and the transition region are attributed to the two distinct adsorption sites of the UPD H and OPD H on the poly-Pt surface.