A novel approach to construct organized structures and tunable electronic properties of poly(3-hexylthiophene) (P3HT) monolayers on Au(111) surfaces was developed based on a self-assembly process in a liquid phase. On a bare Au(111) surface, P3HT adsorbs as a monolayer with a randomly oriented and curvy-wire morphology. When the gold surface was pre-modified by an iodine adlayer (I-Au(111)), the passivation effect of iodine decreases the substrate-adsorbate interaction. As a result, P3HT adsorbs as linear chains, stacking and folding into regular arrays of a polymer bundle. By controlling the electrode at more negative potentials, it is able to desorb the iodine adlayer from the substrate. The remaining P3HT adsorbs onto the Au(111) surface directly, retaining a linear and regular arrangement. However, a different electronic structure is imaged by scanning tunneling microscopy (STM). The scanning tunneling spectroscopy (STS) analysis reveals that this molecular image is associated with a 0.16 eV shift of the Fermi level toward HOMO position, indicating a stronger p-doping characteristic of the adlayer. The phenomenon is ascribed to an iodine-induced p-doping reaction which occurs during the desorption of iodine. This work demonstrates that electrode potential and pre-adsorbed halide adlayers can be effectively used to regulate the arrangement and electronic properties of adsorbed molecules on metallic substrates.