The copper-doped ZnS particles were immobilized on the surface of Hexafluorobutyl acrylate-co-methacrylic acid (poly (HFBA-co-MAA)) which synthesized by bulk polymerization electrospun nanofibers. The fluoropolymer fibers, which have around 200 nm in average diameter, of poly (HFBA-co-MAA) and are obtained by electrospinning. Zinc and copper ions are introduced onto the fiber surface by coordinating with carboxyls of MAA. After that, sulfide ions are incorporated to react with zinc and copper ions by a hydrothermal synthesis. Thus, copper-doped ZnS particles of around 100 nm in average size, are obtained and well loaded on the fiber surface. The absorption of copper-doped ZnS/HFBA-co-MAA fiber composites is at 262 nm and 326 within the ultraviolet light region. It was found that the average rate of H2 evolution of copper-doped ZnS powders slightly decreased, while the average rate of H2 evolution of copper-doped ZnS/HFBA-co-MAA fiber composites increased from the first to the third run. The average rate of H2 evolution using the copper-doped ZnS/HFBA-co-MAA fiber composites as the catalyst achieved 49.04 mL/h in the third run.