Poly (vinyl alcohol) (PVA)/silver (Ag) nanoparticle composites were prepared via heat treatment of a mixture solution of silver nitrate (AgNO3) and PVA. The resultant composites were characterized by infrared spectroscopy (FTIR), X-ray powder diffraction (XRD), transmission electron microscopy (TEM) and differential scanning calorimetry (DSC). XRD results showed that pure phase Ag was obtained in the prepared nanocomposites. They also showed that crystallinity of PVA was largely decreased after the composition with nano-sized Ag. TEM results showed that the Ag particles were in sphere shape with 10-40nm diameter in the as-prepared nanocomposites. DSC results showed that the glass transition temperature of the nanocomposites was enhanced by the incorporation of Ag.