A high-performance hydrogen generation system based on the electrospun polyacrylonitrile (PAN)/Ag/Pd composite nanofibers, which were prepared by microwave reducing the electrospun PAN/AgNO3 nanofibers and followed by a replacement reaction has been demonstrated. The morphology of the as-prepared PAN/Ag/Pd composite nanofibers and the metal nanoparticles on the fibers were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), high resolution TEM (HRTEM), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) measurements. It has been demonstrated that the obtained PAN/Ag/Pd composite nanofibers possess fine morphology and high catalytic activities for H-2 generation from aqueous solution of ammonia borane (NH3BH3, AB). The Hy generation test exhibited that the catalyst had excellent catalytic activity (with turnover frequency (TOF) of 377.2 mol Hy h(-1) (mol Pd)(-1)), good recycle stability and easy-separation from the reaction system. This new kind of nanofibers possesses great potential application for the new clean energy development. (c) 2014 Elsevier B.V. All rights reserved.