The title monomer was synthesized and subsequently polymerized via free radical initiation. The high field H-1-NMR and C-13-NMR spectra were recorded and analyzed in terms of polymer stereochemistry. The H-1-NMR spectrum proved of limited value in this regard but the C-13-NMR spectrum yielded a good deal of useful information. Analysis of the spectra strongly indicated that poly(5-vinyl-1,3-benzodioxole) is an atactic polymer.