Ultrafine copper particles were prepared by the thermal decomposition of a copper formate-poly(2-vinylpyridine) complex. At temperatures above 125°C, a redox reaction occurs where Cu+2 is reduced to copper metal and formate is oxidized to CO2 and H2. The decomposition reaction was studied by thermogravimetric analysis, differential scanning calorimetry and mass spectrometry. Copper concentrations up to 23 wt% have been incorporated into the polymer by this technique. The presence of the polymeric ligand induces the redox reaction to occur at a temperature 80°C lower than in uncomplexed copper formate. Incorporation of the reducing agent (formate anion) into the polymer precursor enables the redox reaction to occur in the solid state. Films of the polymer precursor were prepared and the formation of metallic copper particles were studied by visible and infrared spectroscopy, x-ray diffraction techniques, and transmission electron microscopy. Results from these measurements indicate that spherical copper particles with an average diameter of 35angstrom are isolated within the polymer matrix. The particles are thermodynamically stable at temperatures up to the decomposition of the polymer matrix (≈350 °C), but oxidize rapidly upon exposure air.