1,4-Thioxane and silver triflate form two distinct ionic polymers comprising of tetracoordinate silver(I) cations. In both cases, silver is coordinated by the sulfur atoms of two 1.4-thioxane molecules and by the oxygen atoms of two triflate ions. In structure 1, bridging between Ag+ centers occurs only via the triflate moieties. Structure 2 also contains bridges through the second nonbonded electron pair of the sulfur ligands to give an infinite two-dimensional polymer in the crystal.