A novel class of self-assembling nanoparticles is formed with viologen-resorcinarene cavitands; the association model is strongly controlled by their hydrophobicity. Interestingly, the cavitand assemblies are designed through click chemistry to form self-assembled noncovalently connected aggregates through counterion displacement. The iodide and benzoate ions are utilized as strongly polarizable counterions to induce cavitand self-assembly. The counterion-mediated decrease in hydrophilicity of the viologen-resorcinarenes is the underlying trigger to induce particle formation. These particles can be used as nanocontainers and find their applications in delivery systems.