Poly(olefin sulfone)s have been prepared from (R)- and (RS)-1-octen-3-ol, in which the chiral centers are adjacent to the double bond. The C-13-NMR spectra of the polymers have shown that the stereochemistry of the main chain methine carbon formed in the propagation reaction depended primarily upon that of the side chain chiral carbon within the same residue. The polysulfone of(R)-(-)-1-octen-3-ol is therefore the first partially isotactic polysulfone to be prepared by a free-radical polymerization. Large dispersions of chemical shift and well-resolved fine structure in the C-13-NMR spectra have allowed assignments to be made of sequence and intraresidue effects in isotactic and atactic polymers at the main chain tetrad level.