A novel ternary Ag2CO3/Ag/AgNCO Z-scheme heterojunction with excellent visible-light-driven photocatalytic performance was fabricated. The % O-2(-) and, h(+) were proved to be the photocatalytic active substances for the degradation of Rhodamine B (RhB) in Ag2CO3/Ag/AgNCO. Compared to pristine Ag2CO3 and AgNCO, the enhanced photocatalytic activities of Ag2CO3/Ag/AgNCO could be attributed to the low resistance for interfacial charge transfer and desirable absorption capability. In addition, the Z-scheme photocatalytic mechanism is proved by the discussion of the band structure. This work could offer a new insight into the design and fabrication of advanced materials with Z-scheme structures for the efficient treatment of persistent pollutants in wastewater.