In this paper, we show that functionalization of fibrous materials through coating formation is hindered by the need to preserve the capillary-porous system of the fabric and its drapability. Additionally, such coatings must be resistant to abrasion and washing. We consider ways of solving these problems by analysing the formation of a stable coating based on photoactive titanium dioxide on a polyester fibre material as an example. The purpose of such coatings is to destroy coloured organic contaminants when the fabric is exposed to sunlight. We show that a polyester fabric with a titanium dioxide coating can become highly photochemically active and capable of inhibiting the vital activity of gram-negative bacteria and remaining soft and breathable at the same time. We also determined that depositing a titanium dioxide coating does not reduce the polyester fabric tensile strength. Polyester fabrics with photoactive properties can be widely used as decorative and trimming materials—for housing decoration, production of curtains and other decorative interior design elements.