AbstractThe copper bisdithiolene complexes based on highly extended ligands incorporating fused TTF and thiophene moieties (α‐tdt = tiophenetetrathiafulvalenedithiolate and dtdt = dihydro‐thiophenetetrathiafulvalenedithiolate), were prepared and characterised by cyclic voltammetry and electrical transport measurements. The anionic complexes, (nBu4N)x[Cu(dtdt)2] (1) and (nBu4N)x[Cu(α‐tdt)2] (2), (1<x<2), obtained under anaerobic conditions, can be easily oxidised to the stable neutral state, [Cu(dtdt)2]0 (3) and [Cu(α‐tdt)2]0 (4), just by air or iodine exposure. Although no suitable single crystals of the neutral complexes could be obtained, room temperature conductivities measured in compressed powder pellets show values of σRT in the range of 0.10‐0.40 S/cm, a reasonable high electrical conductivity, for a powder compacted sample (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)