Laser ablation technique has been applied for synthesis of silver nanoparticles in different concentrations of Polyvinyl Alcohol (PVA) aqueous solution. The ablation of high pure silver plate in the solution carried out by nanosecond Q-switched Nd:YAG pulsed laser. X-ray diffraction and transmission electron microscopy have been implemented to explore the particles size. Effects of PVA concentrations on absorbance of the silver nanoparticles were studied as well, using a UV–vis spectrophotometer. The preparation process was carried out for deionized water as a reference sample. The comparison of the obtained results with the reference sample shows that the formation efficiency of nanoparticle in PVA is much higher and particles sizes are also smaller.