The new phase-separation and immobilization technique known as fluorous biphase system (FBS) has become an active topic among researchers in both industry and academia. A series of fluorous biphasic reactions catalyzed by Lewis acid-type metal perfluorooctanesulfonates and metal bis(perfluorooctanesulfonyl)amides are reviewed in this paper. The recent development of fluorous phase transfer catalyst (PTC) is also discussed.