Ir(I)-catalyzed atroposelective hydroarylation of alkynes with 1‑aryl isoquinolines via C-H functionalization was realized. In the presence of 5 mol% of [Ir(cod)Cl]2 and 10 mol% of QUINOX-P (L4), a wide range of axially chiral alkenylated biaryls were obtained in up to 98% yield and 97% ee. Notably, only 1 equiv of alkyne was required to guarantee the high efficiency of this C-H functionalization process. This reaction exhibits excellent functional group tolerance under mild conditions.