Hydrogen (H2) production via photocatalysts utilizing solar energy is crucial for a sustainable, carbon-free economy. Cocatalysts are used to improve efficiency by accelerating electron-hole separation. This article discusses the importance of optimizing active sites for H2 evolution through d–p orbital regulation. Traditionally, adjustments to the d-band configuration of transition metal atoms have been limited. A new strategy involving consecutive d–p modulation was proposed, focusing on Ni–Bx cocatalyst. By tuning the B/Ni ratios in Ni–Bx, the d-band configuration of Ni was optimized, resulting in enhanced H2-evolution activity. The Ni–Bx/CdS photocatalyst achieved a remarkable hydrogen production rate, outperforming other state-of-the-art photocatalysts. The study highlights the potential of this consecutive d–p hybridization strategy for future catalyst design.