Cast-hybrid films composed of polyvinyl alcohol (PVA) and silver nitrate were treated according to three different ways, thermal annealing, UV-irradiation, and chemical reduction by a borohydride solution, to obtain PVA/silver nanocomposite films. The nanostructuration process was studied as a function of the treatment conditions, and discussed as a function of the mobility state of the polymer chains in the nanocomposite matrix during treatment. A homogeneous dispersion of crystalline silver nanoparticles was obtained by thermal annealing above T-g and below T-m and UV-lamp irradiation below T-g. For these two treatments, the major processing parameters were the annealing temperature and time and the UV-exposure time, respectively. For low-conversion rate in Ag(0), the films evolved upon ageing at room temperature. Totally different morphology and Ag(0) conversion were achieved by chemical reduction in a borohydride solution. All the silver ions were reduced into Ag(0), and crystalline silver nanoparticles layers parallel to the film surface were observed after the treatment. This morphology was related to the high-swollen state of the polymer matrix during treatment. (C) 2008 Wiley Periodicals, Inc.