Palladium(II) perfluorooctanesulfonate [Pd(OSO2Rf8)(2)] catalyses the highly efficient Heck reaction in the presence of a catalytic amount of a perfluoroalkylated-pyridine as a ligand in a fluorous biphase system (FBS) composed of toluene and perfluorodecalin. The fluorous phase containing the active palladium species is easily separated and can be reused several times without a significant loss of catalytic activity. (c) 2007 Elsevier B.V. All rights reserved.