Poly(3-vinyl benzothiophene) was synthesized by free radical initiation at 60-degrees and 90-degrees-C. The 300 MHz H-1-NMR spectra revealed that some of the aromatic protons were sensitive to polymer stereochemsistry. The resonance pattern fit a pentad stereosequence distribution for an atactic polymer and was interpreted in those terms. The polymer synthesized at 60-degrees-C was not significantly different in terms of stereochemistry than the polymer synthesized at 90-degrees-C.