Eight new silver chalcogenide clusters with different functional groups in the ligand shell were synthesised and characterised by single-crystal X-ray diffraction. The optical properties of the isostructural clusters [Ag6(S-C6H4-CN)6(PPh3)6] (1) and [Ag6(S-C6H4-NO2)6(PPh3)6] (2) are described and compared. In addition, the reactivity of 1 towards metal salts and Lewis acids was investigated, which led to the compounds [Ag6(S-C6H4-CN)6(PPh3)5] (3) and [Ag14S(S-C6H4-CN)12(PPh3)8][FeCl2(thf)4]3 (4). The sulfur-functionalised cluster [Ag14S(S-C6H4-NCS)12(PPh3)8] (5) has prospects for further reactions and for the immobilisation on gold surfaces. The reactions of silver carboxylates with O,S-bis(trimethylsilyl)-4-hydroxythiophenol and bis(trimethylsilyl) chalcogenides in the presence of tertiary phosphanes lead to the formation of the clusters [Ag23S2(S-C6H4-OSiMe3)15(S-C6H4-OH)3(PPh3)8] (6) and [Ag40Se4(S-C6H4-OSiMe3)32(PPh3)8] (7). Compound 6 can be regarded as a dimer of the described Ag14-clusters in 4 and 5, whereas the inorganic core of cluster 7 has an unusual curved structural motif. The reaction of AgOAc with 4-hydroxothiophenol in the presence of triethylphosphane leads to the assembly of a three dimensional network of [Ag8(S-C6H4-OH)6(PEt3)8](OAc)2 (8) in the crystal structure. A solution of 8 was investigated by ESI mass spectrometry, which resulted in the detection of a series of polynuclear silver thiolates with the general composition [Agn(S-C6H4-OH)n–1(PEt3)2]+.