In this work, we developed a convenient way to immobilize silver nanoparticles on the aminated polyacrylonitrile (PAN) nanofibrous mats by combing the electrospinning technology from complex-containing polymer solution, amination of PAN nanofibrous and electroless plating technique. The resultant composite nanaofibrous mats had been characterized by scanning electron microscopy, energy-dispersive spectrometer, transmission electron microscopy, X-ray diffraction, and Fourier transform infrared spectra analysis. The catalytic activity and stability of these resultant composite nanofibrous mats for the catalytic reactions, including reduction of 4-nitrophenol to form 4-aminophenol, and selective oxidation of benzyl alcohol, were investigated. The resultant nanofibrous mats exhibited high-efficiency, convenient separation, recovery, and cyclic utilization properties.