Ag/AgCl composite nanoparticles/polyacrylonitrile nanofiber films were prepared by electrospinning and subsequent in-situ reduction combining in-situ oxidation strategy. Electrospinning was firstly used to fabricate PAN/AgNO3 composite nanofibers; then the AgNO3 was reduced by in-situ reduction with glycol; finally, an in-situ oxidation between Ag nanoparticles and FeCl3 solution was carried on to prepare the composite nanofiber films. The as-prepared materials can be used as high-performance photocatalysts, taking the advantage of the visible-light activity, flexibility, and high photocatalytic kinetics. The present method is helpful for the development of the high-performance membrane based photocatalysts.