In the present study, a hierarchical Co9S8@ZnAginS heterostructural cage was developed for the first time which can photocatalytically produce hydrogen and degrade organic pollutants with high efficiency. First, the Co9S8 dodecahedron was synthesized using a metal-organic framework (MOFs) material, ZIF-67, as a precursor, then two kinds of metal sulfide semiconductors were elaborately integrated into a hierarchical hollow heterostructural cage with coupled heterogeneous shells and 2D nanosheet subunits. The artfully designed hollow heterostructural composite exhibited remarkable photocatalytic activity without using any cocatalysts, with a 9395.3 mu mol g(-1) h(-1) H-2 evolution rate and high degradation efficiency for RhB. The significantly enhanced photocatalytic activity can be attributed to the unique architecture and intimate-contact interface between Co9S8 and ZnAgInS, which promote the transfer and separation of the photogenerated charges, increase light absorption, and offer large surface area and active sites. This work presents a new strategy to design highly active semiconductor photocatalysts by using MOF materials as precursors and coupling of metal sulfide semiconductors to form hollow architecture dodecahedron cages with an intimate interface.