Poly(vinyl alcohol) (PVA)/silver composite nanofibers were successfully prepared by the electrospinning method. Water-based colloidal silver in a PVA solution was directly mixed without any chemical or structural modifications into PVA polymer fibers to form organic-inorganic composite nanofibers. The ratio of silver colloidal solution to PVA played an important role in the formation of the PVA/silver composite nanofibers. We prepared two different atactic PVA/silver nanocomposites with number-average degrees of polymerization of 1700 and 4000 through electrospinning with various processing parameters, such as initial polymer concentration, amount of silver colloidal solution, applied voltage, and tip-to-collector distance. The PVA/silver composite nanofibers were characterized by field emission scanning electron microscopy and transmission electron microscopy (TEM). TEM images showed that silver nanoparticles with an average diameter of 30-50 nm were obtained and were well distributed in the PVA nanofibers. (C) 2009 Wiley Periodicals, Inc. J Appl Polym Sci 115: 2883-2891, 2010