A novel, easy, and cost-effective synthetic procedure is reported for the production of very highly regioregular poly[3-(4-alkoxyphenyl)thiophene]s by means of oxidative coupling. Four copper complexes were synthesized and used as catalysts to obtain polymers with higher regioregularity compared to the previous oxidative coupling methodologies reported in the literature and similar to that obtained by McCullough and Rieke methods in the synthesis of poly-3-alkylthiophenes. The regioregularity of the synthesized polymers was investigated by UV-Visible characterization on polymer thin films and H-1 NMR analysis. The remarkable potentialities of these polymers have emerged from field-effect transistor mobility measurements operated on devices with bottom-contact configuration and hexamethyldisilazane-treated SiO2 gate dielectric, showing a well-defined p-type field-effect response and maximum mobility values in air higher than 10(-4) cm(2) V-1 s(-1). (c) 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 4351-4360