Textile fabrics were subjected to bio-pretreatment using high-activity laccase from Cerrena unicolor for comparison to standard alkaline scouring and organic absorber of ultraviolet (UV) radiation based on 1,3,5-triazine derivatives. The basic aim of the study was the development of textiles made of natural cellulose fibers (mainly flax or its blends with cotton) to provide barrier properties against UV radiation. Controlled application of enzymatic pretreatment of woven fabrics made of natural cellulose fibers allows for an efficient removal of impurities from these fibers, resulting in the improvement of sorptive properties and good penetration of dyeing agents, UV organic absorbers and other chemical modifiers, into the textile structure. In this way, products with UV-protection properties (ultraviolet protection factor >40) are obtained. These innovative barrier materials can be used for outdoor textiles that protect professional people from harmful effects of UV radiation.