We report a new one-dimensional tube-like atomically precise silver-thiolate polymer–chain. The structure consists of Ag14(SR)18 as the building units. Silver atoms are linked with the thiol ligand to form the one-dimensional structure. The non-covalent interactions like argentophilic and C–H···H–C interactions appear as crucial for the long-range structural arrangement. Electronic structure calculations show its semiconductor-type band structure with a band gap of about 2 eV. Conductivity measurements on the single crystal implies its facile charge transfer pathway along the one-dimensional chain. The variation of conductivity between the single crystal and the drop-cast film implies the role of argentophilic and C–H···H–C interactions in the preferred charge transfer pathway.