The reactions of 3,4-bis(4-pyridinesulfanylmethyl)thiophene (L) with CuI in various solvent conditions led to the formation of four supramolecular isomers containing different solvent molecules, [Cu(L)I]_n (1), {[Cu(L)I]·1/2C₇H₈}_n (2a), {[Cu(L)I]·CHCl₃}_n (2b), and {[Cu(L)I]·CH₂Cl₂}_n (3). The four conformational pseudo-polymorphs are relative to the variable conformations of the new flexible thioether ligand, in which different solvents dramatically influence the conformations and the linking modes of the ligand. In addition, the four complexes 1–3 show structure-related photoluminescent properties.