AbstractEffect of butanol and Triton X‐100 on formation, supramolecular organization and local dynamics of poly(N‐ethyl‐4‐vinylpyridinium)‐dodecyl sulfate complexes have been studied by UV spectroscopy, high‐speed sedimentation, laser light scattering and electron spin resonance (ESR) spectroscopy. It was found that solubilization of butanol promotes aggregation of the complex species in solution and results in contraction of the region in which water‐soluble complexes are formed. On the contrary, highly aggregated complexes disaggregate up to molecularly dispersed state upon addition of Triton X‐100. It was found that under the experimental conditions neither butanol (up to 3 wt%) nor Triton X‐100 ([Triton X‐100]/[sodium dodecylsulfate] ≤ 1:1) cause destruction of the complexes. The results of ESR spin probe and spin label studies show that in both cases supramolecular realignments are accompanied by a slight increase of the local molecular mobility of surfactant ions in the complex micelles, segmental mobility of polyelectrolyte being unchanged. Copyright © 2006 John Wiley & Sons, Ltd.