Enamines and iminium ions are key intermediates in organocatalyst-mediated asymmetric reactions. After the seminal publications of List and MacMillan in 2000, chemistry based on organocatalysts involving an enamine and an iminium ion as an intermediate has developed dramatically. Recent progress in this field is summarized in this chapter. Organocatalyst-mediated domino reaction is a powerful method for the synthesis of complex molecules, and its application for the total synthesis of natural products and medicines in a small number of pots are described. Combination of organocatalyst and other catalysts for the stereoselective syntheses are also summarized.