The four model configurational triads of poly(3-hexylthiophene) (PHT) were synthesized by cross-coupling of the appropriate stannyl and bromo 3-hexylthiophene derivatives, catalyzed by Pd[(C6H5)3P]4. The comparison of H-1 and C-13 NMR chemical shifts of the triads with those of PHT allows the unambiguous assignment of the regiochemistry of the polymer. The NMR data of the triads, in conjunction with the results of force field MMP2 calculations, also give information on the conformational properties of PHT samples of different regiochemistry.