The contact properties between gold and poly(3-hexylthiophene) (P3HT) films having either of two distinct molecular orientations and orderings were investigated. Thermal treatment increased the molecular ordering of P3HT and remarkably reduced the contact resistance at the electrode/semiconductor interface, which enhanced the electrical performance. This phenomenon was understood in terms of a small degree of metal penetration into the P3HT film as a result of the thermal treatment, which formed a sharp interface at the contact interface between the gold electrode and the organic semiconductor.