Novel water-soluble anionic p-tertbutylthiacalix[ 4]arene with propanesulfonate fragments has been synthesized. Alkylation of the lower rim of thiacalixarene in the presence of NaH/THF led to cone conformation instead of the expected 1,3-alternate conformer due to metal template effect. The presence of supramolecular associates at the critical micelle concentration of 1.65 · 10−5 M were investigated in aqueous solutions by a combination of different techniques (DLS and conductivity). It was observed that the macrocyclic platform decreases the CMC by tenfold as compared with non-macrocycle analogs. A simple approach for the design of stable monodisperse Ag-based nanoaggregates (near 95 nm) containing ionic Ag and organic ligand-thiacalixarene sulfo derivative in water has been developed. Self-assembled fractal hybrid nanodendrites consisting of water-soluble anionic (thia)calixarenes and Ag+ have been obtained in a single step under mild conditions. © Springer Science+Business Media Dordrecht 2017.