Abstract1,3‐Di(2‐thienyl)benzene (T13B), 4,4′‐di(2‐thienyl)biphenyl (TBP), and 3,5‐di(2‐thienyl)‐pyridine (T35P) were prepared. Films were deposited on the electrode in the anodic oxidative polymerization of T13B, 1,4‐di(2‐thienyl)benzene (T14B) and TBP, but the oxidation product of T35P did not cover the entire surface of the electrode. The infrared spectra of the films indicated oxidative coupling to occur at the 5 and 5′ positions of the thiophene rings. While the cyclic voltammograms of poly‐T14B were well‐defined, those of poly‐T13B and poly‐TBP had complex shapes with two or three anodic peaks. When the absorption spectra were measured during electrochemical oxidation, new peaks appeared at 2,0 and 1,9 eV for poly‐T13B and poly‐TBP, respectively. The films looked green in the oxidized state and faintly yellow in the neutral state. The green colour was retained without applied voltage in the cell and in the dry state. It was concluded that conjugation along the main chain