A novel photocatalyst, Bi2WO6/NiO/Ag, with hierarchical flower-like Z-scheme heterojunction, which exhibited excellent stability and photocatalytic activity over a wide light spectrum, was firstly synthesized and used in the remediation of real oil sands process water (OSPW) and achieved complete removal of aromatics, classical naphthenic acids (NAs), and heteroatomic NAs after 6 h of photocatalytic treatment. The acute toxicity of OSPW was completely eliminated after only 2 h of treatment. h+ and ∙OH were found to be the major oxidative species in the photocatalytic system. The enhanced photocatalytic efficiency is the result of the unique Z-scheme electron transfer among electron mediators Ag, NiO, and Bi2WO6, which was supported by the in-situ irradiated XPS. The study benefits the design of engineered passive treatment approach for OSPW remediation through solar light-driven catalyst.