Herein, a protocol for the construction of axially chiral biaryls via Pd-catalyzed direct C-H olefination of 1-arylisoquinoline N-oxides through kinetic resolution have been uncovered. The atroposelective C-H olefination of 1– arylisoquinoline N-oxides is achieved with alkenes such as acrylates, styrenes, phenylvinyl sulfone, acrylonitrile, and maleimides. The commercially available, cost-effective, and bench-stable chiral mono- protected amino acid is successfully utilized as the chiral ligand to achieve atroposelective products via kinetic resolution. The high conformational stability of the axially chiral products observed from the DFT calculations, shows their excellent stability. A plausible mechanism has been proposed based on the preliminary mechanistic studies, which was further evidenced by the DFT calculations.