We have developed metal sulfide photocatalysts with various crystal structures and constituent metal cations with d(0), d(5), and d(10) electron configurations. Cu3VS4, Cu3NbS4, and Cu3TaS4 with a sulvanite structure, ZnGaxIn2-xS4 (x = 0-0.6), and MnGaInS4 with layered structures, BaLaCuS3 with a one-dimensionally anisotropic structure along the b-axis, and a (ZnS)(0.9)-(CuCl)(0.1) solid solution with a zinc blende structure have arisen as new photocatalysts for H-2 evolution in the presence of sacrificial electron donors under visible light irradiation.