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The development of durable multifunctional properties is crucial for the production of high-performance technical textiles. In this work, a novel, environmentally friendly and facile method was developed for the chemical modification of cotton fabric by in situ biosynthesis of Ag NPs in the presence of sumac leaf extract as a reducing agent on TiO₂, ZnO and TiO₂ + ZnO previously applied to cotton fibres. The results showed that the presence of TiO₂, ZnO and TiO₂ + ZnO significantly increased the concentrations of the synthesised Ag NPs on the cotton fibres compared to the one-component Ag coating. This resulted in excellent antimicrobial properties of the TiO₂/Ag, ZnO/Ag and TiO₂ + ZnO/Ag composites even after 25 washes. While the TiO₂ and ZnO particles in the composite were incompatible, the synergistic effect among Ag, TiO₂ and ZnO in the composites resulted in excellent UV blocking properties of the coatings before and after 25 washes. Since the biosynthesis of Ag NPs was accompanied by a yellow–brown colouration of the samples, the photocatalytic self-cleaning of the composite coating could not be determined from the photodegradation rate of the coffee stains. This research provides a new environmentally friendly approach to producing durable antimicrobial and UV blocking coatings on cotton fibres.