Band structure engineering is an efficient technique to develop desired semiconductor photocatalysts, which was usually carried out through isovalent or aliovalent ionic substitutions. Starting from a UV-activated catalyst ZnGa2S4, we successfully exploited good visible light photocatalysts for H-2 evolution by In3+-to-Ga3+ and (Cu+/Ga3+)-to-Zn2+ substitutions. First, the bandgap of ZnGa2-xInxS4 (0 <= x <= 0.4) decreased from 3.36 to 3.04 eV by lowering the conduction band position. Second, Zn1-2y(CuGa)(y)Ga1.7In0.3S4 (y = 0.1, 0.15, 0.2) provided a further and significant red-shift of the photon absorption to similar to 500 nm by raising the valence band maximum and barely losing the overpotential to water reduction. Zn0.7Cu0.15Ga1.85In0.3S4 possessed the highest H-2 evolution rate under pure visible light irradiation using S2- and SO32- as sacrificial reagents (386 mu mol/h/g for the noble-metal-free sample and 629 mu mol/h/g for the one loaded with 0.5 wt % Ru), while the binary hosts ZnGa2S4 and ZnIn2S4 (synthesized using the same procedure) show 0 and 27.9 mu mol/h/g, respectively. The optimal apparent quantum yield reached to 7.9% at 500 nm by tuning the composition to Zn0.6Cu0.2Ga1.9In0.3S4 (loaded with 0.5 wt % Ru).