Uniformly dispersed Ag nanoparticles (AgNPs) with diameter about 5 nm embedded in electrospun polyacrylonitrile (PAN) nanofibers were synthesized by using tea polyphenols (TP) as the reductant. The reducing ability of TP toward Ag ions was characterized by Fourier transform infrared spectroscopy and ultraviolet–visible spectra, and the results revealed that TP exhibit satisfied reducing ability in the synthesis process. Transmission electron microscopy observation showed that the synthesized spherical AgNPs with diameter about 5 nm were immobilized on the surface and in the interior of PAN nanofibers by electrospinning technology. The interactions of Ag with PAN and TP were investigated by X-ray photoelectron spectroscopy (XPS), and the results suggested that PAN polymer and TP both served as stabilizer during the synthesis of AgNPs because of the chelating interactions of Ag with cyano groups and phenolic hydroxyls. The synthesized AgNPs in PAN nanofibers exhibit good antibacterial property and may be used for antibacterial and catalytic applications. POLYM. ENG. SCI., 2013. © 2012 Society of Plastics Engineers