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[Display omitted] • Stable functional photocatalyst of BTO@Bi 2 S 3 /PU was successfully fabricated. • BTO@Bi 2 S 3 /PU possess excellent activity for oxytetracycline photodegradation. • Metal ions redox boosted the charge transfer of Z-scheme from BTO to Bi 2 S 3. • ·O 2 − and h+ primarily dominate the photodegradation mechanism of oxytetracycline. • Eco-toxicity tests prove the environmental-friendly of photocatalytic process. Inspired by the high sustainability, energy saving, cleanliness of photocatalysis (PC) with respect to antibiotics decomposition, we developed a stable, highly efficient Bi 2 Ti 2 O 7 @Bi 2 S 3 /polyurethane (BTO@Bi 2 S 3 /PU) photocatalytic system. It exhibited the best degradation performance with the removal of 82.08 % oxytetracycline (OTC) within 180 min under the optimal reaction parameters. Systematic characterization of BTO@Bi 2 S 3 /PU revealed its wider light-harvest capacity, higher electron–hole (e−–h+) separation efficiency, lower interface resistance, and better redox potential in heterojunction. Based on electrochemical characterization and density functional theory calculation, the construction of Z-scheme BTO@Bi 2 S 3 photocatalyst substantially optimized the band structure. Moreover, the redox cycles of Bi3+/Bi5+ and Ti4+/Ti3+ further enhanced the charge transfer rate during the photoactivation process. For the OTC photodegradation pathways, ·OH, h+, ·O 2 −, and 1O 2 dominated the pollutant decomposition and the toxicity of intermediates were decreased. Overall, the BTO@Bi 2 S 3 /PU photocatalytic system may provide a universal and stable technique for advanced photoheterojunction applications and wastewater purification. [ABSTRACT FROM AUTHOR]