Silk fibroin (SF) fibers were modified with sulfonated polyaniline and, via an in situ redox technique, a high density of gold (Au) nanoparticles were supported directly on the surface of the fiber. The morphology, formation, and application of the as-prepared product, Au/ SPANI-modified SF composite fiber, were investigated. By controlling the concentration of HAuCl 4 , the density of Au nanoparticles on the composite fiber could be effectively adjusted. It is suggested that sulfonated polyaniline contributes to the generation of a high density of Au nanoparticles supported on the SF fibers. The composite fiber exhibited good activity when taking the reduction of pnitrophenol as a model reaction.