CuS nanoflowers were loaded on anatase TiO2/polyvinylidene fluoride (PVDF) fibers by hydrothermal treated electrospun tetrabutyl orthotitanate (TBOT)/PVDF fibers at low temperature. The results indicated that the amount of copper source and sulfur source determined the crystallization and morphology of the resultant products. It was found that the composite of CuS narrowed the band gap energy of TiO2 and enhanced the separation efficiency of the photogenerated electron-hole pairs of TiO2. The photocatalytic reaction rate of CuS/TiO2/PVDF fibers to rhodamine B was 3 times higher than that of TiO2/PVDF fibers under visible light irradiation. Besides, owing to the preparation process was carried out at low temperature, the flexibility of CuS/TiO2/PVDF fibers was ensured. In addition, the self-cleaning performance of the dye droplets on the resultant product surface was demonstrated under visible light. Meanwhile, the resultant product can automatically remove dust on the surface of the material under the rolling condition of droplets due to its hydrophobicity. Therefore, the as-prepared CuS/TiO2/PVDF fibers can not only degrade the contaminated compounds, but also depress the maintenance cost owing to its self-cleaning performance, which means a very practical application prospect.