We report the study of the supramolecular assemblies formed by the incorporation of quaternary ammonium cations such as Me4N+ or Et4N+ into host-guest assemblies with p-sulfonatocalix[4]arene in the presence of a lanthanide(III) cation in water. We use microcalorimetry to characterize the formation of these supramolecular assemblies. We obtain a molecular description of these assemblies by performing molecular dynamics simulations over a very large period of time. The structures of these supramolecular complexes have been determined and discussed through specific interaction energy contributions. By combining MD simulations and (HMR)-H-1 spectroscopy, we highlight a specific behavior of the supramolecular assembly with the Me4N+.