Many organic/inorganic nanocomposites have been fabricated into fibrous materials using electrospinning techniques, because electrospinning processes have many attractive advantages and the ability to produce relatively large-scale continuous films. In this study, the polyvinyl alcohol (PVA)/silk/titanium dioxide (TiO2) nanocomposite self-cleaning textiles were successfully produced using electrospinning technique. After optimizing electrospinning conditions, we successfully obtained the PVA/silk/TiO2 nanocomposite fibers with average diameter of similar to 220 nm and TiO2 concentration can be as high as 18.0 wt.%. For the case of the PVA/silk/TiO2 nanocomposite textile, the color of brilliant green coated on the textile surface changed from the initial green color to colorless after ultraviolet (UV) irradiation. Because of its worthy photocatalytic performance, the developed PVA/silk/TiO2 nanocomposite materials in this study will be beneficial for the design and fabrication of multifunctional fibers and textiles.