A facile approach of preparing well-dispersed silver nanoparticles (Ag NPs) which fabricated on surface of porous silicon (PSi) generating Ag NPs/PSi chip and the catalyses towards reduction of nitro aromatics are described in detail in this work. Aqueous silver ions are reduced readily by the surface Si-H-x (x = 1, 2 or 3) species of PSi within dozens of seconds at room temperature. The resulted Ag NPs are demonstrated by scanning and transmission electron microscopes, ultraviolet-visible spectrum and X-ray powder diffraction. A proposed mechanism of forming Ag NPs on PSi chip is discussed in light of the observed phenomena and the analyses of infrared and energy dispersive X-ray spectra. The stably porous architecture of PSi and the well-dispersed Ag NPs on PSi surface guarantee the highly catalytic activities of the Ag NPs/PSi chip. The progresses of reducing nitro aromatics catalyzed by the Ag NPs/PSi chip in the presence of sodium borohydride are traced by ultraviolet-visible measurements to estimate the catalytic performance of the Ag NPs/PSi chip. (C) 2014 Elsevier B.V. All rights reserved.