ReBr(CO)(3)(3,3`-disubstituted-2,2＇-biquinoline) complexes modified with diphenylzine (Ph2Zn) and methylaluminoxane (MAD) were employed in the polymerization of styrene (St). The results show that both the initiating activity and the characteristics of the polystyrenes (PSts) are independent of the different conformational rhenium complexes. Studies made using W-vis spectroscopy agree with a dissociation of the biquinoline ligand when MAO is added to the reaction system.