The amine-bridged calix[4]arene is available via the introduction of an azide group into the meta position of the macrocyclic skeleton followed by thermal decomposition. While further modification of the amine bridge by the alkylation reactions was proved to be problematic, the acylation reactions led smoothly to the expected N-acyl products. As shown by NMR spectroscopy, unusual dynamic behaviour of these compounds can be attributed to their restricted rotation around the amide C–N bond, leading finally to the desymmetrization of the whole molecule in the ¹H NMR spectra at low temperatures (slow exchange conditions). Further substitution of the proximal aromatic units of acylated amine-bridged calix[4]arene with bromine atoms leads to inherently chiral systems with hindered rotation at room temperature.