Removal of organic contaminants in wastewater using sunlight-driven photocatalysts has received significant attention in recent years. However, the rational design of photocatalysts to attain high light absorption, lower charge carrier recombination with efficient photocatalytic activity and good recycling capability is crucial for the practical photocatalysis process. Herein, solid-state Z-scheme BiOCl0.6I0.4/α-Ag1.82Cu0.09WO4 heterojunction is synthesized by assembling hierarchical 3D-BiOCl0.6I0.4 nanoflowers on cube-like 3D-α-Ag1.82Cu0.09WO4 surface through a hydrothermal method. A wide range of characterization techniques confirms the successful synthesis of BiOClxI1−x (0 ≤ x ≤ 1.0), α-Ag1.82Cu0.09WO4 and BiOCl0.6I0.4/α-Ag1.82Cu0.09WO4 binary composites. The TC antibiotic removal efficiency of 30 wt% BiOCl0.6I0.4/α-Ag1.82Cu0.09WO4 binary composite reaches 95.91% within 120 min under natural sunlight irradiation and the rate constant is 1.81 and 3.33 times higher than the pristine BiOCl0.6I0.4 and α-Ag1.82Cu0.09WO4, respectively. The optimized binary heterojunction exhibits excellent photocatalytic performance for toxic pollutants like MB (η = 97.27%) and RhB (η = 95.75%) under direct sunlight irradiation. The favorable photocatalytic activity of binary heterojunction is ascribed to enhancing the sunlight absorption range, the tight contact interface and the effective separation of electron/hole pairs. Notably, 30 wt% BiOCl0.6I0.4/α-Ag1.82Cu0.09WO4 binary composite exhibits attractive recycling ability and good photostability for prolonged sunlight irradiation. Furthermore, the total organic carbon results also confirm that the 30 wt% BiOCl0.6I0.4/α-Ag1.82Cu0.09WO4 efficiently mineralized the model pollutants (TC antibiotic, MB and RhB) into other unharmful compounds under sunlight irradiation. In summary, this work offers an effective strategy to prepare solid-state Z-scheme heterojunction with favorable photocatalytic activity, which can increase wastewater purification efficiency.