Regarding poly(vinyl alcohol)/silicotungstic acid (PVA/H4SiW12O40) gel as precursor, the silver nanoparticles (NPs) were selectively deposited on the surface of the PVA/H4SiW12O40 nanofibers by using electrospinning and photoreduction methods. X-ray photoelectron spectroscopy, Fourier transformation infrared spectroscopy, and UV-vis diffuse reflectance spectroscopy were used to affirm the structure and formation of tri-component nanohybrids. Field environmental scanning electron microscope and transmission electron microscopy indicate that the average diameter of silver NPs was changed from 25 nm to 50 nm, with decreasing the relative concentration of SiW12 in the as-electrospun nanofibers. The nanocomposites exhibit excellent photocatalytic activity in degradation of Rhodamine B. This result arises from the synergistic effects and the large specific surface areas of Ag/PVA/H4SiW12O40 tri-component nanohybrids. (C) 2012 Elsevier B.V. All rights reserved.