Several cationic rhodium(I) complexes [Rh(COD)L(2)][C(5)(CF(3))(5)] have been synthesized through substitution of the weakly bound [C(5)(CF(3))(5)](-) ligand from [Rh(COD)(C(5)(CF(3))(5))], further emphasizing its unique reactivity. Besides acetonitrile, pyridine derivatives with varying degrees of fluorination have been employed as ligands in order to investigate the influence of fluorination upon the binding affinity towards the resulting [Rh(COD)](+) fragment and the limit as to which the [C(5)(CF(3))(5)](-) ligand can be displaced. Furthermore, the newly synthesized compounds represent rare examples of rhodium complexes containing fluorinated pyridines as ligands.