The effect of macrocycle size on the association of supramolecular amphiphiles composed of 4-sulfonatocalix[n]arene and 1-methyl-3-tetradecylimidazolium (C(14)mim(+)) was studied in aqueous solutions at pH 7. When the cavitand contained four sulfonatophenol units (SCX4), formation of spherical nanoparticles (NPs) was observed. By-contrast, both supramolecular micelle (SM) and NP formation could be attained in the presence of NaCl when the larger, more flexible 4-sulfonatocalix[8]arene (SCX8) served as the host compound. The SCX8-promoted self-assembly into the SM was enthalpically more favorable than the NP production, but the molar heat capacity changes in the two processes barely differed. An addition of 50 mM NaCl significantly increased the enthalpy of C(14)min(+)-SCX8 NP formation, thereby making the self-organization into the SM more favorable. The transformation of SM into NP at high temperatures was due-to the substantial entropic contribution to the driving force behind the NP formation. The critical micelle concentration (cmc) and the local polarity in the headgroup domain were considerably lower for the SM compared with those of the conventional C(14)mim(+)-Br- micelle: