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Photocatalytic solar energy conversion to hydrogen is sustainable and attractive for addressing the global energy and environmental issue. Herein, a novel photocatalytic system (NiS/Ni 3 S 4 cocatalysts modified mesoporous TiO 2 ) with superior photocatalytic hydrogen evolution capability through the synergistic im- pact of NiS/Ni 3 S 4 (NiS x ) cocatalyst and efficient hole scavenger has been demonstrated. The photocatalytic hydrogen evolution of TiO 2 –NiS x hybrids with the different content of NiS x and upon different organic hole scavengers was both investigated. The hybrid of TiO 2 decorated with 3％ (mole ratio of Ni 2 + ) NiS x co- catalyst in methanol solution showed the optimal photocatalytic hydrogen evolution rate of 981.59 μmol h ? 1 g ? 1 which was about 20 times higher than that of bare mesoporous TiO 2 . Our results suggested that the boosted hydrogen production performance is attributed to both the improved photoinduced electrons migration between NiS and Ni 3 S 4 in cocatalyst and the high hole captured efficiency by hole scavengers of methanol.