Silver(I) complexes with trimethylphosphine and perfluorinated carboxylates of the general formula [Me3PAgOOCR](2), where R = C2F5, C3F7, C6F13, C7F15, C8F17, C9F19, C6F5 and Me3PAgOOC(CF2)(3) have been prepared and their thermal decomposition studied. Thermal decomposition proceeded in multistages, starting with the detachment of carboxylates and followed by trimethylphosphine dissociation. The final product was metallic silver. The temperatures of silver formation were in the 473-633 K range. Complexes were characterised by C-13, F-19, P-31 NMR and vibrational spectra. Spectral analysis favoured Ag(I) trigonal coordination with unidentate trimethylphosphine and bidentate carboxylates forming bridges between silver(I) ions.