Polythiophene films synthesized by electrochemical polymerization under various conditions were undoped and redoped maximally with iodine. The electrical conductivity of the redoped films was in the range 2 × 10 2 − 5.9 S cm −1. Vibrational spectra of the undoped films were analysed on the basis of those of model compounds including 2,2′-bithiophene, 2,2′:5′,2″-terthiophene and 2,2′:5′,2″:5″,2′-quaterthiophene. First, the intensity ratio of the infrared CH out-of-plane bending bands at 697 (2-substituted thiophene) and 787 cm −1 (2,5-substituted thiophene) is a clue to the degree of polymerization. Secondly, the intensity ratio of the infrared double-bond symmetric and antisymmetric stretching bands reflects the distribution in length of the conjugated segment. Finally, the intensities of three Raman bands at 1155, 682 and 652 cm −1 give information about the amount of distorted structure around the inter-ring C-C bonds. From the comparison of the spectroscopic and conductivity data, it is concluded that a high degree of polymerization alone is not adequate for a doped film to have high electrical conductivity but abundance of long conjugated coplanar segments is the requisite condition.