New p-tert-butylthiacalix[4]arenes functionalized with hydrazides of nicotinic, isonicotinic, 3-nitrobenzoic acids, 2-hydrazinopyridine, phenylhydrazine, benzotriazole groups at the lower rim in cone, partial cone and 1,3-alternate conformation have been synthesized. The mechanism of self-assembly of supramolecular nanosized particles based on functionalized p-tert-butylthiacalix[4]arenes with silver nitrate and or dicarboxylic acids (oxalic, malonic, succinic acid) has been determined by dynamic light scattering . For the first time, it has been shown that nanoscale particles based on p-tert-butylthiacalix[4]arenes, capable of recognizing metal cations and dicarboxylic acids can form cascade or commutative three-component supramolecular systems. Also for the first time, it has been shown that p-tert-butylthiacalix[4]arenes containing N-substituted hydrazide and heterocyclic fragments are coreceptors, capable of simultaneously binding silver (I) cations and dicarboxylic acids. The formation of cascade systems: “macrocycle-silver (I) nitrate-dicarboxylic acid” is a characteristic of p-tert-butyl thiacalix[4]arenes containing N-substituted hydrazide fragments.