Methods used in organic synthesis and within the chemical industry as a whole in the 21st century aim to conform to the principles of green sustainable chemistry (GSC) and, from now on, the realization of GSC in the chemical industry will be an important task. Synthetic organic chemistry aims to establish waste-free and environmental-benign industrial processes using highly versatile Lewis acids. Although aluminum chloride, boron trifluoride, titanium tetrachloride, etc. are known as Lewis acids, they need to be used stoichiometrically or in excess to achieve high yield and high selectivity. Furthermore, they are rarely recovered and recycled. Thus, even though they are widely used industrially, these Lewis acids cause many unresolved problems, including the production of large amounts of wastes and the high consumption of energy. We attempted to develop highly active Lewis acid catalysts and to use these catalysts in GSC-type reaction processes. Our procedure was, first, to develop highly active Lewis acid catalysts, and then to meet the challenge of creating revolutionary organic reaction processes using fluorous solvents and water as reaction media. The key technological aim of the development was to achieve a “catalyst recycling system that utilizes the high activity and structural features of fluorous Lewis acid catalysts”.We developed the novel fluorous Lewis acid catalysts, ytterbium (III), tin (IV), hafnium (IV) bis (perfluoroalkanesulfonyl) amide or tris (perfluoroalkanesulfonyl) methide catalyst. Our catalysts were effective and recyclable for Baeyer-Villiger reaction, direct esterification, and transesterification in fluorous biphasic system (FBS). The cyclodextrin copolymer-inclusion complex of our catalyst and the fluorous silica gel-supported catalyst were also effective and recyclable for Diels Alder reaction, Mukaiyama-aldol reaction and Baeyer-Villiger reaction in water.