Photocatalytic solar energy conversion to hydrogen is sustainable and attractive for addressing the global energy and environmental issue. Herein, a novel photocatalytic system (NiS/Ni3S4cocatalysts modified mesoporous TiO2) with superior photocatalytic hydrogen evolution capability through the synergistic impact of NiS/Ni3S4(NiSx) cocatalyst and efficient hole scavenger has been demonstrated. The photocatalytic hydrogen evolution of TiO2–NiSxhybrids with the different content of NiSxand upon different organic hole scavengers was both investigated. The hybrid of TiO2decorated with 3% (mole ratio of Ni2+) NiSxcocatalyst in methanol solution showed the optimal photocatalytic hydrogen evolution rate of 981.59 µmol h−1g−1which was about 20 times higher than that of bare mesoporous TiO2. Our results suggested that the boosted hydrogen production performance is attributed to both the improved photoinduced electrons migration between NiS and Ni3S4in cocatalyst and the high hole captured efficiency by hole scavengers of methanol.