A water-soluble pillar[5]arene, decafunctionalized with thioether and carboxylate fragments, was synthesized as a structural analogue of Sugammadex. Its ability to restore the contraction of the diaphragm muscle by encapsulating the muscle relaxant rocuronium bromide was demonstrated. Using UV-vis, NMR and fluorescence spectroscopy, it was shown that the muscle relaxant is associated with the pillar[5]arene with an association constant of 4500 M⁻¹ and a stoichiometry of 1 : 1. The structure of the inclusion complex of the pillar[5]arene with rocuronium bromide was additionally investigated by quantum chemical methods.