Silver coated aminated polyacrylonitrile (Ag/APAN) nanofibrous composite membranes were prepared by a facile method that combined the electrospinning technique and electroless plating method. Amine modification was used to replace the environment-unfriendly sensitization, activation pretreatment used in traditional electroless plating and modify the surface of PAN nanofibers to prepare the aminated PAN (APAN) nanofiers, then electroless silver plating was applied on APAN nanofibrous surface to prepare Ag/APAN nanofibrous composite membranes. Scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD) and Fourier transform infrared (FTIR) spectroscopy were used to characterize the morphology and structure of APAN and Ag/APAN nanofibrous membranes. The results demonstrated that Ag+ can be adsorbed on the APAN nanofibrous surface and reduced into metallic silver clusters by the amino group. These little amount of silver clusters acting as catalytic active centers can ignite the next electroless plating process resulting in silver layers deposited uniformly on the surfaces of APAN nanofibers. The prepared Ag/APAN nanofibrous composite membrane exhibited excellent catalytic performance in the reduction of o-nitroaniline with sodium borohydride as reducing agent and did not cause secondary pollution of the reaction system.