Electrospinning is the most common technique for fabricating polymer fibers as well as nanoparticles embedded polymer fibers. Silver selenide nanoparticles were synthesized using tri-n-octylphosphine (TOP) as solvent and tri-n-octylphosphine oxide (TOPO) as capping environment. Silver selenide was prepared by reacting silver nitrate and selenium with tri-n-octylphosphine (TOP) to form TOP-Ag and TOP-Se solutions. Both absorption and emission spectra signify the formation of nanoparticles as well as the TEM which revealed spherical particles with an average particle size of 22 nm. The polymer, PVP used was prepared at concentrations ranging from (35 to 45 wt%) and the TOPO-capped silver selenide nanoparticles (0.2 and 0.6 wt%) were incorporated into them and electrospun by varying the voltage from 11 to 20 kV. The SEM images of the Ag2Se/PVP composite fibers revealed the fibers of diameters with average values of 425 and 461 nm. The X-ray diffraction results show peaks which were identified due to alpha-Ag2Se body centered cubic compound. The sharp peak observed for all the samples at 2 theta=44.5 suggest the presence of Ag in the face centered cubic which can be attributed to higher concentration of silver nitrate used with molar ratio of selenium to silver and the abundance of silver in the silver selenide crystal. Fourier transform infrared spectroscopy, thermogravimetric analysis (TGA) and ultraviolet-visible spectroscopy were used to characterize the structure of the PVP/Ag2Se composite fibers. (C) 2015 Elsevier Ltd. All rights reserved.