In this study, Z-scheme BiOCl/Bi2WO6 heterojunctions with enriched oxygen vacancies (OVs) were fabricated. Enhanced separation efficiency of photogenerated electron-hole pairs from BiOCl/Bi2WO6 composite was confirmed through surfacephotovoltagespectroscopy (SPS), photocurrent and electrochemical impedance spectroscopy (EIS) analysis. Photocatalytic decontamination of rhodamine B (RhB) and tetracycline (TC) over BiOCl/Bi2WO6 composite was investigated, and BiOCl/Bi2WO6 heterojunctions reveal higher photocatalytic performance than BiOCl and Bi2WO6. The boosted activity of BiOCl /Bi2WO6 heterojunctions stems from the improved separation rate of carriers. In view of electron paramagnetic resonance (EPR) results and band structures of BiOCl and Bi2WO6, photocatalytic mechanism of the BiOCl/Bi2WO6 heterojunctions follows Z-scheme mechanism.