Abstract The interest to determine the ionization degree of counterion initiates the need to study the relationship between counterion binding constant (RX Br) and the growth of self-assembly micellar structure. This paper discussed the microscopic evidence for the correlation of counterion binding constant values and micellar structure of cationic surfactants in the presence of phenolates and 2-ethyl phenolates ions in flexible nanoparticle (FN)-system of ionized phenyl salicylate-catalyzed piperidinolysis. The sizes of micelles were determined by particle size analysis. Transmission electron microscopy (TEM) results showed a spherical micellar structure for phenolates and 2-ethyl phenolates ions at counterion binding constant values 6.3 ± 1.0 and 24.0 ± 1.1 respectively. A study using a semi-emperical kinetic technique in published article proved that the suggested micellar structures at respective counterion binding constant values corresponded with the present microscopic evidence.