In the search for new synthetic routes toward greener and more facile syntheses of conjugated polymers, C–H functionalization provides a promising solution by minimizing the production and processing of aryl halide monomer precursors used in traditional organometallic coupling reactions. In this paper, we investigate the use of Au(I) and its ability to directly C–H activate 2-bromo-3-hexylthiophene to form a reactive monomer species, bypassing the typical Grignard monomer formation from a dihalogenated thiophene. Addition of Pd-PEPPSI-iPr as a palladium catalyst source in the presence of the resultant aurylated thiophene monomer yielded poly(3-hexylthiophene) as observed by both NMR and GPC. Studies on the growth of these polymers show linear dependence between Mn and monomer conversion, low dispersities, as well as Mn predicted by catalyst loading, which is supportive of a living-type chain growth mechanism. This Au–Pd system represents a novel methodology for incorporating C–H activation into the synthesis of P3HT with control over Mn.