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Oxygen vacancies and its associated defect states have a great influence on the electronic and structural aspects of semiconductor photocatalysts, yet there is paucity of investigations about the influence of the defect states on their photocatalytic properties. Herein, this study reports the hierarchical fabrication of oxygen vacancy enriched ZnO/ZnMn 2 O 4 /ZnS-PVA nanocomposite (NCs) for the enhanced photodegradation of rifampicin and co-trimoxazole. The formation of lattice expansion induced oxygen vacancies and its associated Urbach tail energy, and n-p-n heterojunction-based S-scheme charge transfer path synergistically contributed to the boosted photocatalytic performance of the as prepared NCs. The photocatalytic performance of the nanomaterial towards rifampicin and co-trimoxazole has been determined to be 80% and 90% under visible light irradiation, respectively. Furthermore, various operating parameters including the concentration of NCs and drug, pH and interference of various ions have been evaluated. The degraded product intermediates have been elucidated by GC-MS analysis. The toxicity of the as-prepared nanomaterials has been evaluated by treating the samples with root tips of Allium cepa , where the NCs was found to be non-toxic. The study provides a new-fangled insight on the preparation and fabrication of non-toxic and defect rich nanomaterials which may help stimulate this area of research. [Display omitted] • ZnO–ZnMn 2 O 4 –ZnS assembled nanocubes has been synthesized using a facile coprecipitation method. • Correlation among the Urbach tail energy and enhanced photocatalysis has been established. • Effects of various environmental factors have been evaluated systemically. • QSAR method has been exploited for intermediate toxicity evaluation. • A thermodynamically feasible charge transfer path has been proposed. [ABSTRACT FROM AUTHOR]