Reaction of the potassium salt of the N-thiophosphorylated thiourea Et 2 NC(S)NHP(S)(OiPr) 2 (HL) with a mixture of AgNO 3 and PPh 3 in aqueous EtOH/CH 2 Cl 2 leads to the mixed-ligand silver(I) complex [Ag(PPh 3 ) 2 {Et 2 NC(S)NP(S)(OiPr) 2 }] ([Ag(PPh 3 ) 2 L]). Recrystallization of [Ag(PPh 3 ) 2 L] from an acetone/n-hexane mixture leads to the decomposition of the starting complex with the formation of [Ag(PPh 3 ){Et 2 NC(S)NP(S)(OiPr) 2 }] ([Ag(PPh 3 )L]), [Ag(PPh 3 ) 3 NCS]∙(CH 3 ) 2 C=O and Et 2 NP(S)(OiPr) 2 . The structures of [Ag(PPh 3 ) 2 L], [Ag(PPh 3 )L], [Ag(PPh 3 ) 3 NCS]∙(CH 3 ) 2 C=O and Et 2 NP(S)(OiPr) 2 were all investigated by IR, 31 P{ 1 H} and 1 H NMR spectroscopy, and their compositions were established by elemental analysis. The crystal structure of the complex [Ag(PPh 3 ) 3 NCS]∙(CH 3 ) 2 C=O obtained from single crystal X-ray diffraction is presented.