Reaction of silver(I) trifluoromethanesulfonate with tetrakis(methylthio)tetrathiafulvalene (TMT-TTF) yielded polynuclear silver(I) complex [Ag(TMT-TTF)(O3SCF3)]. The compound crystallizes in the orthorhombic system, space group Pbam with cell constants a = 14.855(5), b = 22.510(3), c = 13.310(8) Angstrom, Z = 8. It is a neutral 1 : 1 metal/ligand complex in which each Ag(I) ion is six-coordinated by four sulfur atoms from the bridging TMT-TTF and two oxygen atoms from the bidentate O3SCF3 anion, which results in a two interwoven polymeric chain structure. It represents the first example of the silver(I) ion coordinated directly to TTF-derivatives. The compound is an insulator at room temperature but behaves as a semiconductor when doped with iodine.