The solution polymerizations of acrylamide (AAm) initiated by the photoinitiator DAROCUR 2959 (DAR) and UV light were studied. The kinetics of acrylamide polymerization in the presence of silver salt was investigated. Dilatometry was implemented to follow continuously the fast photopolymerization. The polymerization rate vs conversion curve of the photopolymerization of AAm was described by two nonstationary-state intervals. The abrupt increase in the initial rate was attributed to the accumulation of the reaction loci. The continuous decrease in the polymerization rate with conversion was discussed in terms of the increased termination based on the intra- and intermolecular chain transfer to polymer. The deactivation of the excited states of initiator and initiating radicals by their interaction with reaction products (silver nanoparticle-polymer nanocomposites) is also taken into account. The irradiation of silver salt and AAm led to the formation of silver-polymer nanocomposites. The small silver nanoparticles grow during the photolysis (or polymerization and storing) to microparticles and large agglomerates.