AbstractThe microstructural transition of aqueous 0.1 M cetylpyridinium chloride (CPC) in the combined presence of salt KBr and long chain alcohol (C9OH‐C12OH) has been studied as a function of alcohol concentration, electrolyte concentration and temperature. The viscosity of the CPC/KBr micellar system showed a peaked behavior with alcohol concentration (C0), due to alcohol induced structural transition, which was confirmed by dynamic light scattering (DLS) and rheological analysis. Besides C0, the chain length of alcohol (n) was found to show a remarkable effect on the micellization behavior of CPC/KBr system. It was observed that the ability of alcohol to induce micelle growth diminishes with n, which was well supported by viscosity, rheology and DLS measurements. To examine the effect of the electrolyte on the micellar growth, the salt concentration was varied from 0.05 to 0.15 M and it was observed that with increase in [KBr], the peak position shifts towards lower C0. The effect of temperature on the micellar system showed interesting phase behavior for CPC/KBr/Decanol. The system exhibited a closed solubility loop with an upper critical solution temperature (UCST) > the lower critical solution temperature (LCST), reminiscence of nicotine‐water system. The role of surfactant head group on the structural evolution was revealed by comparing the present results with our previous report for similar micellar system, CTAB/KBr/long chain alcohol.