A novel poly(aryleneethynylene), in which the main chain and the tetrathiafulvalene (TTF) side chains are coplanar, has been prepared and characterized. The polymer can self‐assemble in tetrahydrofuran (THF) and the π‐extended coplanar backbones adopt good face‐to‐face stacking, which is confirmed by X‐ray diffraction (XRD) analysis. Cyclic voltammetry has revealed that the polymer has reversible electroactive properties. The optical bandgap deduced by UV‐vis absorption spectroscopy and the electrochemical bandgap are 2.03 and 2.14 eV. The conductivities of the powder and the realigning solid of the polymer are 6 × 10−8 and 4 × 10−6 S cm−1.
