Biphasic Wacker-oxidation of a series of linear alkenes (from hexene-1 up to dodecene-1) and styrenes catalysed by water soluble calixarene-based systems has been studied. The substrate selectivity is shown to vary significantly depending on the calixarene used. The water soluble palladium(II) complexes with the calixarenes modified by the benzonitrile groups are shown to exhibit higher activity as compared to the same for similar catalytic systems containing a palladium salt and a water soluble calixarene. (C) 2004 Elsevier B.V. All rights reserved.