Silver(I) complexes with triethylphosphine and perfluorinated carboxylic acids residues of general formula [Et3PAgOOCR](2), where R=C2F5, C3F7, C6F13, C7F15, C8F17, C9F19, C6F5 and Et3PAgOOC(CF2)(3)COOAgPEt3, were synthesized. Thermal decomposition proceeded in two stages - both exothermic processes corresponding to the elimination of carboxylate and triethylphosphine residues. The final product of the thermal decomposition was metallic silver. Analyses by C-13, F-19, P-31 NMR spectroscopy and vibrational spectra suggest trigonal coordination of Ag(I), the coordination sphere consisting of unidentate triethylphosphine and bidentate carboxylates forming bridges between metal ions.