This study is to investigate the role of the coating of TiO2 nanoparticles deposited on wool fibers against high-intensity ultraviolet B (UVB), ultraviolet A (UVA), and visible light irradiation. The properties of tensile and yellowness and whiteness indices of irradiated TiO2-coated wool fibers are measured. The changes of TiO2-coated wool fibers in optical property, thermal stability, surface morphology, composition, molecular structure, crystallinity, and orientation degree are characterized using diffuse reflectance spectroscopy, thermogravimetric analysis, scanning electronic microscopy, energy-dispersive X-ray spectroscopy, Fourier-transform infrared spectroscopy, and X-ray diffraction techniques. Experimental results show that the tensile properties of anatase TiO2-coated wool fibers can be degraded under the high-intensity UVB, UVA, and visible light irradiation for a certain time, resulting in the loss of the postyield region of stress–strain curve for wool fibers. The coating of TiO2 nanoparticles makes a certain contribution to the tensile property, yellowness and whiteness indices, thermal stability, and surface morphology of wool fibers against high-intensity UVB, UVA, and visible light irradiation. The high-intensity UVB, UVA, and visible light can result in the photo-oxidation deterioration of the secondary structure of TiO2-coated wool fibers to a more or less degree. Meanwhile, the crystallinity and orientation degree of TiO2 coated wool fibers decrease too.