Organocatalysis is a new and fast growing research area, especially for asymmetric synthesis. Compared to metal catalysis and biocatalysis, organocatalysis has a number of unique features such metal-free, mild reaction conditions, novel mode of activations, and good structural amenability. Fluorous organocatalysis provides an efficient way for catalyst recovery. In addition to phase tag separation, fluorous chain can also be used to modify the reactivity and selectivity in the design of new catalysts.