Pyrroles substituted by nitronyl nitroxide (1-3) have been prepared and the ground state multiplicity of their cation diradicals have been examined. The tripler was found to be the ground state for 2(+.), 3(+.), although the triplet signal was not observed for 1(+.). The ground state spin multiplicity of these cation diradicals was rationalized in terms of the exchange interaction between unpaired electrons which reside SOMO and SOMO’ of these species, respectively. A novel approach to polaronic high spin polymers obtained from 1,3-phenylene-bis(2’-1H-pyrrole) is also mentioned.