Catalytic asymmetric cross-dehydrogenative coupling (CDC) reactions have been recognized as one of the most direct and efficient methods for the construction of C–C bonds. This chapter summarizes and discusses the outstanding achievements that have been made in the field of enantioselective CDC reactions, a powerful method to couple one C(sp³)–H bond α to a nitrogen, oxygen, or carbonyl group and various C(sp)–H, C(sp²)–H or C(sp³)–H bonds under oxidative conditions. Various catalytic systems including well-defined organometallic complexes, small organic molecules, and enzymes could be applied to promote this type of novel transformation. Undoubtedly, the asymmetric CDC reactions have attracted intensive attention because they provide waste-minimized access to construct versatile and useful enantioenriched frameworks rapidly and efficiently.