Biphasic Wacker-oxidation of higher olefins, catalyzed by palladium complexes with water-soluble sulfonated calix[4]arene- and calix[6]arene-derived ligands have been studied. Complexes showed high catalytic activity under mild conditions and can be multiply reused. Catalysts display substrate selectivity in oxidation of C-6 and C-8 olefins-intemal cavity of calixarenes recognizes the size of the substrates. The correlation between binding constants of inclusion complexes and selectivity has been established. (C) 2002 Elsevier Science B.V. All rights reserved.