Me3SiCH2COOAg, [Ag(Me3SiCH2COO)(PPh3)] and [Ag(Me3SiCH2CH2COO)(PPh3)] were prepared and characterized in solution by 1H, 13C, 29Si, 31P and 29Si, 31P CPMAS NMR. Spectral analysis suggests bidentate bridging carboxylates and monodentately bonded PPh3 in solution and in the solid state. Two crystallographically inequivalent molecules of PPh3 appeared in the solid state, what is evident from 31P CPMAS NMR. Thermal studies of both complexes demonstrate two stage decomposition process (exothermic followed by endothermic) with formation of metallic silver in the range 483-548 K. TGA/IR and MS studies of Me3SiCH2COOAg and [Ag(Me3SiCH2COO)(PPh3)] revealed volatile products of decomposition (CO2, Me3 Si-) and recombination reactions such as (Me3SiCH2CO)2O, (Me3Si)2O. The mechanism of complexes thermal decomposition is proposed.