3-ethynylthiophene was polymerized with [Rh(COD)acac], [Rh(NBD)acac] and [Rh(NBD)Cl]2 homogeneous catalysts and heterogeneous catalyst [Rh(COD)Cl]2/PBI prepared via anchoring [Rh(COD)Cl]2 on porous polybenzimidazole.