Silver nanoparticles well dispersed in a spherical Poly(vinylpyrollidone)(PVP) matrix were simply prepared by spray pyrolysis of aqueous solutions of AgNO3 and PVP without any reducing agent. Highly monodisperse silver particles were obtained above the initial mass ratio of PVP/AgNO3 ∼ 1 and in a certain narrow temperature range. Below the critical mass ratio the silver particles grew to larger ones polydispersely. As the ratio increased above it, they became smaller maintaining their monodispersity. The use of PVP considerably decreased the reduction temperature of the silver nitrate from 450 °C to 250 °C under the same pyrolysis conditions, due to its reducing nature. As the pyrolysis temperature increased above the decomposition temperature of PVP, the silver particles in the matrix grew to merge to a single particle while their crystallite size did not increase as much. The spherical assemblies of the silver nanoparticles were hardly disengaged even after severe washing off the matrix materials. The mechanism of the nanoparticle growth was also discussed.