Ag-coated polyacrylonitrile (PAN) nanofibers have been prepared by a novel, facile and green way that combined electrospinning technique and poly(dopamine)-assisted electroless plating method. Poly(dopamine) (PDOP) was formed by oxidation polymerization of dopamine on the surface of PAN nanofibers to promote the electroless plating of silver. Scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), attenuated total reflectance Fourier transform infrared (ATR FT-IR) spectroscopy and energy dispersive X-ray spectroscopy (EDS) were used to characterize the morphology and structure of Ag/PDOP/PAN nanofibrous composite membrane and Ultraviolet-visible (UV-vis) Spectroscopy was used to investigate its catalytic performance. The results indicated that silver clusters composed of face-centred cubic crystal Ag with average crystallite size of about 18 nm were well distributed on the surface of dopamine-modified electrospun PAN nanofibers (PDOP/PAN). The prepared silver coated PDOP/PAN (Ag/PDOP/PAN) nanofibrous composite membrane exhibited an outstanding catalytic performance, and showed good reusability for completely degradating methylene blue (MB) dyes and reducing o-nitroaniline very quickly, respectively.