[en] The radiolytic method is particularly suitable for generating metal nanoparticles in solution. The ability to control metal particle size, size distribution, morphology, geometry and dispersion as part of the synthetic process directly translates to an ability to design the material properties so that the final product is specifically tailored to its designated function such as optical devices. Polymers are excellent host materials for nanoparticles of metals and semiconductors. As a result new properties can arise from interaction between macromolecules and particles. Thus investigation on formation pathways of small metal crystallites in polymers can yield knowledge useful in advancing the synthesis of novel materials. A radiolytic technique is used to prepare two types of nanocomposites with Ag, PVA/Ag by film casting and PVA hydrogel/Ag nanocomposites by radyolitically reduction of Ag ions in hydrogel matrix. Using differential scanning calorimetry (DSC) the melting behavior and kinetics of the PVA/Ag nanocomposites are investigated and compared to those of pure PVA. The melting as well as crystallization behavior of polymers is crucial because it ultimately governs its thermal properties, impact resistance and stress strain properties. Understanding the melting behavior is significant not only to tailor the properties of nanocomposites but to understand the nature of the interactions between the constituents. Models from Jeziorny, Ziabicki and Ozawa suitable for non-isothermal crystallization kinetics are adopted to investigate melting kinetics of pure PVA and PVA/Ag nanocomposites. There are strong dependences of the degree of crystallinity (X_c), peak melting temperature (T_m), half time of melting (T₁/2) and Ozawa exponent (m) on the Ag content and the heating rate. The activation energy of melting (E) calculated with Kissinger model is markedly changing with the content of Ag in nanocomposite and with the preparation route. In terms of the obtained melting kinetics results, the interaction between the constituents is discussed