The present study describes non-covalent interaction and complexation behaviour of sodium ascorbate (SA) with cucurbituril (CB) at neutral pH in aqueous Na2SO4 solution. The interaction behaviour is investigated using various analytical techniques like NMR, UV–Vis, fluorescence, TGA and DRS. The substantial increase in the intensity of emission and absorption spectra of sodium ascorbate is observed. The Benesi–Hildebrand evaluation method is used to determine the stoichiometry and equilibrium constant of the cucurbituril–sodium ascorbate complex, which suggested the 1:1 complex. Time-dependent 1H NMR, 13C CP MAS and CD studies also echoed non-covalent interaction between SA with CB. © 2016 Informa UK Limited, trading as Taylor & Francis Group.