Monosubstituted pillararenes containing a phosphonate fragment were successfully obtained in good yields. It was found that the introduction of bulky fragments containing tetra-coordinated pentavalent phosphorus atoms prevents self-Assembly of monosubstituted pillararenes and the formation of supramolecular polymers. Pillararenes with phosphonate and 1-Aminophosphonate substituents demonstrated recognition towards Na +, K +, Cs + and Pb 2+. Their ability to form complexes with these cations was evaluated by UV spectroscopy. Dynamic light scattering (DLS) revealed the formation of aggregates with K +, Cs + and Pb 2+. It was established that the substituent at the α-carbon atom of the aminophosphonate fragment played a significant role in Pb 2+ binding. DLS and transmission electron microscopy revealed that Pb 2+-induced aggregation formed particles with a monodisperse distribution of 0.02-0.23 and a hydrodynamic diameter of 58-178 nm.