The changes in the morphology and structure of silver carboxylates during thermal and photochemical decomposition were investigated using TEM, x-ray diffraction, and DTA. Thermal and photochemical decomposition of long chain silver carboxylates were both found to form nano-sized silver particles (3–5 nm). This type of metallic silver formation can be directly attributed to the layered structure of the solid state structure of the [Ag(O₂C_nH_2n−1)]₂ dimers in the crystalline lattice. In addition, this type of metallic silver was observed to be influenced by the organic by-products formed, which can hinder the addition of new silver atoms to the growing metal crystallite.