An easy synthetic procedure for soluble poly[3-(4-alcoxyphenyl)thiophene]s is reported. The polymers present a high regioregularity degree as determined by both UV-vis spectra and H-1 and C-13 NMR analysis. Furthermore, X-ray powder diffraction analysis performed on films of the polymers suggests a pi-stacked packing structure of the macromolecules. Electrical characterization was performed on one of the synthesized polythiophenes on both undoped and doped (with FeCl3 or iodine) films. The conductivity and charge-carrier mobility were assessed by current-voltage and field effect measurements. Well-structured polymer films were obtained simply via spin coating from chloroform solutions and without the need of further processing, unlike other regioregular polythiophenes reported in the literature. (c) 2007 Wiley Periodicals, Inc.