High-molecular-weight poly(vinyl alcohol) (PVA)/sodium alginate (SA)/silver nanocomposite was successfully prepared via electrospinning technique. Water-based colloidal silver in a PVA/SA blend solution was directly mixing without any chemical and structural modifications into PVA/SA matrix to form an organic-metallic nanocomposite. The effect of the addition of silver colloidal solution on the PVA/SA/silver nanocomposite was investigated through a series of experiments varying molecular weight of PVA and electrospinning processing parameters such as concentration of PVA solution, PVA/SA blend ratio, applied voltage, and tip-to-collector distance. In the case of PVA with number-average degree of polymerization of 1700, by increasing the amount of SA in spinning solution, the morphology was changed from fine uniform fiber to beaded fiber or bead-on-string fiber structure. Increase of the amount of silver colloidal solution resulted in higher charge density on the surface of ejected jet during spinning, thus more electric charges carried by the electrospinning jet. As the charge density increased, the diameter of the nanocomposites became smaller. Transmission electron microscopy images showed that the dense silver nanoparticles were well separately dispersed in PVA/SA matrix. Energy-disperse X-ray analysis indicated that carbon, oxygen, natrium, and silver were the principle element of PVA/SA/silver nanocomposite. (C) 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 1916-1926, 2009