TiO₂ nanofibers decorated with Pt and Pd nanoparticles have been synthesized and studied in various photocatalytic processes. Excellent photocatalytic behavior in the decomposition of organic dyes in water, degradation of organic stains on the surface of flexible freestanding cellulose/catalyst composite films and in generation of hydrogen from ethanol using both suspended and immobilized catalysts are demonstrated. The performance of the nanofiber-based TiO₂ materials is competitive with—and in some cases outperforms—their conventional nanoparticle-based counterparts. In all cases, Pd-decorated TiO₂ nanoparticles and nanofibers proved to be more efficient than their Pt-based counterparts, which could be explained on the basis of the formation of nano-sized Schottky interfaces at the contacts between TiO₂ and metal nanoparticles. The feasibility of forming cellulose/catalyst composites provides a novel way of utilizing photocatalyst materials in large-area coatings and freestanding films.