The title polymer was synthesized by free radical initiation in bulk and its H-1-NMR and C-13-NMR spectra were recorded and analyzed in terms of polymer stereochemistry. The aliphatic region of the proton spectrum shows an unusual multiplicity due to stereochemical sensitivity and the resonances of several of the ring carbons displayed a sensitivity to higher order stereosequences. The analysis of these spectra showed that poly(5-vinyl-2,2’-thiophene) is an atactic polymer.