A silver–acrylate nanocomposite was prepared using a novel one-pot strategy involving eosin dye as visible sensitizer and an amine derivative as radicals' source. The mechanism highlighted by steady state photolysis and time-resolved absorption spectroscopy lies on the initial formation of a strong ion-pair complex between eosin and Ag+. Upon visible irradiation, the excited triplet state of the metal complex efficiently abstracts a hydrogen atom from the amine and produces an α-aminoalkyl radical. In acrylate monomer matrix, such a strong reactive species initiates a free radical photopolymerization and also provides the reduction of the silver cation. Through this ‘in-situ’ fabrication method, the kinetics formation of the nanocomposite and its detailed structural analysis are characterized by UV–visible, real-time FTIR absorption spectroscopy and by transmission electron microscopy.Graphical abstract