Poly(3-methylthiophene) (PMeT) electrosynthesized by direct oxidation of 3-methylthiophene in boron trifluoride diethyl etherate (BFEE) has been studied by Raman spectroscopy in the temperature scale of 123-458 K. Experimental results demonstrate that the thermal stability of PMeT in the oxidized state is much lower than that of the polymer in the neutral state. Furthermore, during the cooling process, the conformation of neutral species changes from a coil-like state into a rod-like state, while the conformation of the oxidized species does not change.