In this paper the electronic and optical properties of various poly(3-alkylthiophene)s differing in alkyl chain length were investigated. And their dependence on temperature were also investigated. The electrical conductivity decreased with the increase of alkyl chain length. In addition optical properties were changed due to the shift of edge energy which was caused by the change of the alkyl chain length and rise of temperature. The conformational change of poly(3-alkylthionphene) depending on the alkyl chain length is believed to be responsible to the change of electronic and optical properties of materials.