Silver clusters too small to support a plasmon band possess interesting fluorescence properties as well as being a convenient route to studying the early stages of nanoparticle formation. Fluorescent silver clusters are synthesized in toluene solution, and the formation is monitored herein by laser flash photolysis (LFP). Kinetic analysis of the formation of the Ag clusters is consistent with the formation of the smallest possible clusters, silver dimers (Ag-2), whereby a mechanism for the formation of these clusters is provided as well as the first reported extinction coefficient and association constant for Ag-0 to form Ag-2. The formation of Ag-2 clusters is contrasted with the formation of Ag nanoparticles in aqueous media, and the particular stability and selectivity toward Ag-2 in this system is also studied using LFP.