The enantioselective conjugate addition (ECA) of nucleophiles to electron-deficient alkenes represents one of the most powerful methods to form Csingle bondC or C-heteroelement bonds, which is widely used in total synthesis of complex chiral molecules. Dealing with the metal-catalyzed version, significant breakthroughs were accomplished in the past two decades, notably through the design of new chiral ligands and the evaluation of a large series of metal catalysts. Numerous challenging transformations were successfully achieved such as ECA of vinylic, alkynyl, silicon, and phosphorus nucleophiles, the formation of quaternary stereogenic centers or the addition to polyenic Michael acceptors. As presented along this chapter, the copper-catalyzed ECA was intensively studied over the past 20 years; nevertheless, other metals (Ni, Pd, Rh, or lanthanoides) have been progressively introduced. Less commonly used metals such as Ru, Ir, Cd, Fe, Zr, Hf, Zn, Mg, Co, Ca, Ba, Sr, and alkalis, were also examined, which often led to remarkable results.