The Wacker oxidation of olefins was studied in the presence of catalyst systems composed of a water-soluble calixarene (sulfonated and oligo glycidyl calixarenes), a palladium salt, and a copper salt. It was shown that the addition of calixarenes accelerates the reaction of linear alkenes-1 when the substrate size corresponds to the calixarene cavity size(calix[4]arenes for hexene-1 and calix[6]arenes for octene-1). It was found that the optimal reaction temperatures were 50degreesC and 60degreesC for calix[4]arenes and calix[6]arenes, respectively. In the oxidation of substituted styrenes, the activity of the catalyst systems also depended on the fitting of a substrate molecule to the calixarene cavity.