The two distinct adsorption sites and transition between the under and over-potentially deposited hydrogen (UPD H and OPD H) on the polycrystalline iridium (poly-Ir) surface in the 0.2 M LiOH electrolyte have been studied using the phase-shift method. At the forward and backward scans, the UPD H peak occurs on the cyclic voltam-mogram. The transition region on the phase-shift profile or the Langmuir adsorption isotherm occurs at ca. -0.80 to -0.95 V vs. SCE. At the transition region (-0.80 to -0.95 V vs. SCE), the equilibrium constant (K) for H adsorption transits from $7.9 imes10^{-2};to;1.5 imes10^{-4}$ and vice versa. Similarly, the standard free energy $({Delta}G_{ads})$ of H adsorption transits from 6.3 to 21.8kJ/mol and vice versa. The UPD H and OPD H on the poly-Ir surface act as two distinguishable electroadsorbed H species. 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-Ir surface.