Abstract Ytterbium perfluorooctanesulfonate [Yb(OPf) 3 ] catalyses the highly efficient Henry reaction in the presence of a catalytic amount of a novel perfluoroalkylated-pyridine as a ligand in a fluorous biphase system (FBS) composed of toluene and perfluorodecalin. An unprecedented chemoselective addition of aldehydes among various carbonyl compounds and the robustness of the catalytic system for recycling using by simple phase-separation were obtained.