Effective proton conductors based on calix(4)arene sulfonic acid and CX3COOH (where X = H, F, Cl) with molar ratio 1:1 were obtained in crystalline form. It was demonstrated that the original calixarene sulfonic acid and its complex with CCl3COOH, and complexes with CH3COOH and CF3COOH have pairwise similar structures and similar proton transport patterns. (C) 2017 Elsevier B.V. All lights reserved.