The first regiochemical analysis of self-doped polythiophenes is presented. Regioregularity is as signed based on the H-1 and C-13 NMR spectra of sodium poly(3-(3-thienyl)propanesulfonate) (1) and sodium poly(6-(3-thienyl)hexanesulfonate) (2) to particular configurational diads and triads, using one-and two-dimensional nuclear Overhauser effect (NOE), double quantum filtered homonuclear correlational spectroscopy (DQF-COSY), and heteronuclear multiple-quantum coherence (HMQC) experiments. Excellent resolution enhancement of peaks is obtained with a Gaussian multiplication. An estimate of the relative populations of the configurational triads in these polymers is thereby obtained. The ratio of HT to HH diads in both 1 and 2 is 4:1, based on the areas associated with the aromatic NMR signals.