The one-dimensional copper(I) coordination polymers Cu-3{MeSi(CH2SMe)(3)}(2)X-3 (X = Cl, Br) and [{MeSi(CH2SMe)(3)}Cu(NCMe)]Y (Y = OSO2CF3, BF4, PF6) were readily obtained in very good to excellent yields (80-95%) by reacting CuX or [Cu(NCMe)(4)]Y, respectively, with the tridentate thioether ligand MeSi(CH2SMe)(3) in acetonitrile. The new complexes were characterized by a combination of analytical and spectroscopic techniques, including electrospray ionization mass spectrometry and, for the bromo and hexafluorophosphate derivatives, single-crystal X-ray diffraction. Both complexes exhibit one-dimensional chain structures with approximately tetrahedral copper centers and bridging unibentate/bidentate thioether ligands.