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.