A series of silver triphenylphosphine complexes containing pyridyl chacogenolate (S, Se) ligands has been synthesized by employing [AgCl(PPh3)3] and [Ag2(μ-Cl)2(PPh3)4]. The complexes [Ag(S-4-pyH0.5)2(PPh3)2] (1) and [Ag2(μ-S-4-py)2(PPh3)4] (2) were obtained by the reactions of [Ag2(μ-Cl)2(PPh3)4] with 4-pySH in the presence of Et3N and NaOH, respectively. The former has a hydrogen-bonded chain-like structure, while the latter possesses a discrete binuclear structure. 2 on heating in methanol afforded a two-dimensional coordination polymer, [Ag2(μ-S-4-py)2(PPh3)2]n (3). The reaction of [Ag2(μ-Cl)2(PPh3)4] with NaSe-4-py gave [Ag3(μ-Se-4-py)3(PPh3)4] (4) as the primary product together with a minor mononuclear complex, [Ag(Se-4-py)(PPh3)3] (5). The latter could be obtained in excellent yield under the same conditions utilising [AgCl(PPh3)3] as the starting material. Complex 5 on recrystallization afforded 4. The reaction of [AgCl(PPh3)3] with NaS-2-py yielded [Ag(S-2-py)(PPh3)3] (6). Complexes 2-6 on refluxing in chloroform gave insoluble polymeric complexes of composition [Ag(Epy)]n (7) (Epy = 4-pyS (7a), 4-pySe (7b), 2-pyS (7c)) which on thermolysis yielded Ag2E (E = S, Se). The molecular structures of these complexes (1-6) have been established unambiguously by single-crystal X-ray diffraction analyses. Non-bonding interactions in the molecular structures have been discussed. © The Royal Society of Chemistry 2015.