This chapter summarizes the recent achievements in the area of asymmetric functionalization reactions of C–H bonds via a transient carbon–metal (C–M) species (focusing on contributions after 2009). Compared with the traditional cross-coupling reactions, where C–X and C–M bonds are coupled, mediated by transition metal complexes, these reactions employ C–H bond containing compounds as the coupling partner, thus reducing the synthetic steps and minimizing the formation of salt wastes. Fueled by an array of effective transition metal-based catalytic systems bearing different chiral ligands, diverse enantioenriched products containing central, planar, or axially chiral elements can be synthesized via asymmetric C–H bond functionalization reactions. Some biologically relevant natural products can be also accessed in a straightforward manner.