AbstractA membrane electrode selective to hexadecylpyridinium bromide was used to study the micellization of the surfactant in the presence of varying concentrations of crown ethers 15‐crown‐5, dicyclohexyl‐18‐crown‐6 and dicyclohexyl‐24‐crown‐8 at 27°C. The critical micelle concentration of surfactant was largely influenced by the crown ethers used, indicating their participation in the structure of the resulting micelle. The degree of attachment of crown ethers to the surfactant in the micellar structure was found to be 1. An estimation of the Kffor the 1:1 surfactant‐crown interaction in the micellar region is reported. The degree of counter ion dissociation was found to increase with the crown ether concentration, and with the nature of macrocyclic ligands in the order 15‐crown‐5