The photoelectrochemical (PEC) water splitting performance is conventionally limited by the process of photogenerated carrier separation and transport. This work provides an innovative strategy by combination of the spin-polarized electric field and homogeneous junction to address this critical issue. In this work, it finds that a spin-polarized electric field can be fabricated in the CdS photoanode with cubic phase by S vacancy intervention. Furthermore, after controlling the annealing temperature to reach 500 °C, cubic phase CdS photoanode translates to hexagonal phase by localized, forming a homogeneous junction CdS photoanode. By the synergy, the optimized CdS photoanode achieves a photocurrent density exceeding ∼5.0 mA/cm2 for hydrogen evolution under 100 mW/cm2 white light illumination, a 2.4-fold improvement over the performance of the unoptimized photoanodes. Thus, this work provides a novel method to regulation of the photogenerated carrier separation and transport processes for sulfur-based semiconductor photoelectrodes.