Polymerization of butadiene sulfone was accomplished by using two different methods. The first method involves electrochemical polymerization of the monomer using the constant potential electrolysis technique. Oxidation of the monomer under nitrogen atmosphere in an acetonitrile-tetrabutylammonium tetrafluoroborate system yields brown, tarry polymers. On the other hand, the second initiation method, which was radiation polymerization, yields white, powdery polymers. Structural analyses of the two polymers by various spectroscopic methods suggest a structure consisting of two different units in different proportions.