The effect of alkali halides (NaBr, NaCl, KCl) on the interactions between the cationic gemini surfactant hexylene-1,6-bis(dodecyldimethylammonium bromide) (12-6-12) and the anionic polyelectrolyte sodium polyacrylate (NaPAA) in aqueous solution has been investigated by fluorescence emission spectroscopy, UV transmittance, zeta potential, and transmission electron microscopy (TEM). With increased addition of NaBr, a counterbalancing salt effect on the critical aggregation concentration (CAC) is observed. At low concentrations, NaBr facilitates the formation of micelle-like structures between surfactant and polyelectrolyte and results in a smaller CAC. At high concentrations, NaBr screens the electrostatic attraction between surfactant and polyelectrolyte and leads to a larger CAC. Upon the formation of micelle-like structures at high surfactant concentrations, the addition of NaBr is favorable for larger aggregates. The microstructure detected by TEM show that a global structure is generally formed in the presence of NaBr. The interactions also depend on ion species. Compared to NaBr, the addition of NaCl or KCl yields a smaller CAC. (c) 2006 Elsevier Inc. All rights reserved.