Aryl alkenes represents one of the most widely occurring structural motif in countless drugs and natural products, and direct C−H functionalization of aryl alkenes provides atom‐ step efficient access toward valuable analogues. Among them, group‐directed selective olefinic α‐ and β‐C−H functionalization, bearing a directing group on the aromatic ring, has attracted remarkable attentions, including alkynylation, alkenylation, amino‐carbonylation, cyanation, domino cyclization and so on. These transformations proceed by endo‐ and exo−C−H cyclometallation and provide aryl alkene derivatives in excellent site‐ stereo‐selectivity. Enantio‐selective α‐ and β‐ olefinic C−H functionalization were also covered to synthesis axially chiral styrenes.