The new donor ligand 4,5-bis(2-pyrazylmethylsulfanyl)-4′,5′-bis(cyanoethylthio)tetrathiafulvalene (1) has been synthesized and characterized. The electrochemical properties of the ligand have been investigated by cyclic voltammetry (CV) and 1 shows two reversible oxidation processes at E11/2=0.69VandE21/2=0.97V (in DCM, versus Ag/AgCl). The charge-transfer complex (1 2 ) 2+ [(I 2 ) 3/2 I − ] 2 ·2CH 2 Cl 2 has been prepared by layer diffusion and characterized by X-ray crystallography. The oxidized ligand forms head-to-tail π-dimers which are embedded in layers of a 2D polyiodide network. The separation of these dimers by the anionic network and solvent molecules accounts for the insulating property of the charge-transfer complex.