Reactions of a flexible dithioether ligand, 2,3-bis(5-methyl-1,3,4-thiadiazole-2-thiomethyl)quinoxaline (L), with AgX (X = ClO₄ˉ or PF₆ˉ) lead to the formation of two new one-dimensional (1D) silver(i) complexes: {[AgL](ClO₄)}_∞ 1 and {[Ag₂L(CH₃OH)](PF₆)₂(CH₃OH)}_∞ 2, which have been characterized by elemental analysis, IR spectroscopy, and X-ray crystallography. Although 1 and 2 are synthesized under the same conditions, they take different structures due to the difference in anions in the silver salts. In 1, each ligand supplies three N-donors to bridge two silver atoms to result in a chain structure, and all silver atoms in the chain possess the same coordination geometry. In 2, each ligand gives six N-donors to coordinate to two silver atoms of different geometries, forming a 1D chain. The changes in counteranions affect the coordination mode of the ligand and the geometry of the Ag(i) centre, and consequently give rise to complexes with different structures. The coordination features of the ligand have also been primarily investigated through density functional theory calculations.