The accelerated kinetic behaviour of charge carrier transfer and its unhindered surface reaction dynamic process involving oxygenated-intermediate activation and conversion are urgently required in photocatalytic water (H₂O) overall splitting, which has not been nevertheless resolved yet. Herein, localized CdS homojunctions with optimal collocation of high and low index facets to regulate d-band center for chemically adsorbing and activating key intermediates (*-OH and *-O) have been achieved in H₂O overall splitting into hydrogen. Density functional theory, hall effect, and in situ diffuse reflectance infrared Fourier transform spectroscopy confirm that, electrons and holes are kinetically transferred to reductive high index facet (002) and oxidative low index facet (110) of the localized CdS homojunction induced by facet Fermi level difference to dehydrogenate *-OH and couple *-O for hydrogen and oxygen evolution, respectively, along with a solar conversion into hydrogen (STH) of 2.20 % by Air Mass 1.5 Global filter irradiation. These findings contribute to solving the kinetic bottleneck issues of photocatalytic H₂O splitting, which will further enhance STH.