The interactions between negatively charged diblock polyelectrolyte PDMA(71)-b-PAA(59),) and oppositely charged gemini surfactant hexylene-1,6-bis(dodecyldimethylammonium bromide) (12-6-12) in basic media were studied using dynamic light scattering, fluorescence spectroscopy, Surface tension, and H-1 NMR. With increased addition of surfactant, the conformation of polyelectrolyte experienced changes from the initial unimer with open-extended PAA block, to the nano-scaled aggregates/complexes with a maximum hydrodynamic diameter (D-h), and finally to the stable complexes with a smaller Dh. Accordingly the value of Dh during the whole process of increasing the surfactant concentration changed from 14-17 nm, to 184 nm, and to the final 70 nm, respectively. This transformation was driven by the electrostatic attractive/repulsive interactions, the hydrophobic interaction between hydrophobic surfactant tails, and the hydrophilicity of PDMA block. (C) 2009 Elsevier Inc. All rights reserved.