Poly( 3-hexylthiophene) has been renowned for having excellent electrochemical reactivity and optoelectronic functionalities. The existence of a pre-peak pair at similar to 0.7V in the polymerization CV could be noticed in several references. Because this pre-peak pair is almost enveloped into the broad main peak pair. Especially the existence of them in the CV obtained from monomer free electrolyte is hardly noticed. There have been many different interpretations for the existence of the pre-peak pair. This research was to examine the appearance of the pre-peak by using new approach of electrocasting of polymer from solution.