Asymmetric catalytic C–C coupling reactions via C–H bond activation are currently among the most attractive and powerful tools in synthetic organic chemistry. In the past few decades, a variety of catalytic asymmetric C–C coupling reactions via C–H bond activation have been reported. Compared with traditional asymmetric C–C bond formation reactions, C–H activation/C–C coupling strategies have more advantages in terms of power and cost-effectiveness. In this review, after a short introduction of C–H activation/C–C coupling reactions, recent studies on C–H activation/C–C coupling reactions are reviewed, with an emphasis on enantioselective cross-dehydrogenative-coupling, C–H activation/olefin coupling reactions, hydroacylation of aldehydes via C–H activation, as well as C–H activation/R–X(M) coupling reactions.