The Ag2S nanoparticles embedded in polyacrylonitrile (PAN) fibers matrix were successfully prepared by the combining electrospinning with the hydro(solvo)thermal process, without the presence of any templates or organic surfactants. What's more, the size and content of Ag2S nanoparticles was tunable through proper controlling of the reaction conditions. Consequently, the Ag2S nanoparticles with 10-100 nm diameter could be obtained via this two-step synthetic route. The as-synthesized composites nanofibers were investigated by X-ray diffraction(XRD), field-emission scanning electronic microscopy (FE-SEM), transmission electron microscopy (TEM), selected-area electron diffraction (SAED), Fourier transform infrared spectroscopy (FT-IR), and photoluminescence(PL), respectively. What's more, a possible formation mechanism of Ag2S nanoparticles grown on PAN nanofibers was also proposed. (C) 2011 Elsevier B.V. All rights reserved.