In order to attain reliable information on the structuration and organization of macromolecules participating to interphases in multicomponent materials, it is necessary to use polymers of well defined characteristics in terms of molecular weight, molecular weight distribution and microstructure. This paper describes the synthesis and characterization of a series of polybutadienes, using deuterated monomers in particular. The obtaining of the latter from 2,5-dihydrothiophene-1,1-dioxide and their subsequent polymerization will be described together with some of the characteristics of the resulting polymers.