Fluorous chemistry is a new tool for solution-phase high throughput organic synthesis. Based on the high affinity of perfluoroalkyl chains toward fluorous surfaces and solvent, fluorous separation techniques can significantly facilitate the isolation and purification of intermediates and products. Tagging organic compounds with a light fluorousgroup such as a perfluorooctyl (C8F17) or a perfluorohexyl (C6F13) group followed by product purification using fluorous solid-phase extraction (FSPE) has found increasing synthetic uses. The combination of fluorous methodology with chemoenzymatic approaches can further enhance synthetic and purification process. We have successfully applied a temporary FBoc linker and FSPE technique in the chemoenzymatic synthesis of HS oligosaccharides.