P3HT (Poly(3-hexylthiophene)) is an organic polymer that shows promise as an active material in semiconducting electronics. It is important to study the electronic properties of this material in order to determine its efficacy in such devices. However, many current studies of thiophene only examine the oligomer, since it is a simpler material to investigate. In this study, several P3HT interfaces were analyzed to determine their electronic properties. The P3HT was deposited on Au, highly-ordered pyrolitic graphite (HOPG), and indium tin oxide (ITO) substrates via electrospray deposition. The depositions were performed in several steps, with x-ray photoemission spectroscopy (XPS) and ultraviolet photoemission spectroscopy (UPS) measurements taken between each step without breaking the vacuum. The resulting series of spectra allowed orbital line-up diagrams to be generated for each interface, giving detailed analysis of the interfacial properties, including the charge injection barriers and interface dipoles. The results, when compared to similar oligomer-based investigations, show a difference in the orbital line-up between oligomeric and polymeric P3HT junctions.