Recently, the synthesis of the first pyrrole unit covalently bonded by a diether aliphatic chain to a cobaltabisdicarbollide unit [3,3’-Co(8-C4H4N-(CH2)2-O-(CH2)2-O-1,2-C2B9H10)(1’,2’-C2B9H11)]- [1]- has been carried out in our research group. Polymerization through the  positions of the pyrrole unit is possible in compound [1]-. Direct polymerization of [1]- has been performed either galvanostatically and potentiodynamically without supporting electrolyte. Results obtained from XPS analysis confirmed the in-depth uniformity of the polymer, which has been shown to be self-doped. The proton atoms supply the positive charges required to compensate the negative charges brought by the negative pendant arms in the polymer chain. Copolymerization of [1]- with pyrrole in 1:1 ratio was also carried out. The resulting copolymer had similar physical properties but better electrochemical response with regard to poly[1]. In the two cases (polymer and copolymer) the resulting material was demonstrated to act as an overoxidation-stable cation exchanger with the electrolyte.