A key strategy to improve photocatalytic reaction efficiency is to achieve effective separation and migration of photo-generated carriers. Heterojunctions and co-catalysts are essential for boosting charge separation and transfer, reducing activation energy, and providing active sites for surface redox reactions. Herein, we introduce a composite catalytic system based on NiTiO3, enhanced with Graphdiyne (GDY) and NiP, achieving a hydrogen production activity of 8.37 mmol g−1 h−1. This performance is attributed to the combined effects of S-scheme heterojunction formation and NiP nanoparticle generation through phosphorylation. The S-scheme heterojunction effectively separates electron-hole pairs, reducing charge transport distance. Additionally, NiP nanoparticles formed in situ promote faster charge separation from NiTiO3 and act as active sites to accelerate the reduction half-reaction. Consequently, NiTiO3/GDY-P exhibits higher light absorption, faster charge separation, and superior redox capacity compared to NiTiO3. This work presents an efficient, eco-friendly multiphase catalytic system based on an S-scheme heterojunction and metal phosphide.