Abstract: Surface pretreatment of polyester knitted fabric was carried out using plasma technology. Nano-TiO₂ was loaded on the surface of the polyester knitted fabric, and then Se nanospheres (SeNPs) and Se nanowires (SeNWs) were grown on the surface of the TiO₂/polyethylene terephthalate (PET) through molecular assembly method. Se@TiO₂ binary composite structure was constructed on the surface of the PET (SeNPs@TiO₂/PET and SeNWs@TiO₂/PET). The crystal structure, surface morphology, chemical composition, photocatalytic and antibacterial properties of the material were characterized by SEM, XRD, XPS, UV-vis, PL, and photocatalytic and antibacterial experiments. Characterize the wetting performance of composite photocatalytic materials through contact angle testing. The results indicate that SeNPs@TiO₂/PET and SeNWs@TiO₂/PET composite photocatalytic materials have been successfully prepared. The photocatalytic degradation experiment shows that SeNWs@TiO₂/PET has a higher degradation rate under sunlight simulation. After 90 min of degradation of the model pollutant methylene blue, the degradation rate reached 98.3%. PL spectrum indicates SeNWs@TiO₂/PET separation rate of electron hole pairs is higher than SeNPs@TiO₂/PET. The UV-vis spectrum indicates that relative bandgap widths of SeNPs@TiO₂/PET and SeNWs@TiO₂/PET are 2.8 eV and 2.7 eV, respectively. The antibacterial rates of composite materials against S. aureus and E. coli can reach over 99% and 90%, respectively.