Exploration of novel chiral pharmaceutical candidates is motivation to immersive efforts among synthetic chemists. Achieving skeletal construction and chiral diversity in a highly efficient manner is a momentous goal in the chemical society. Unfortunately, current methods for chiral induction focus primarily on a specific site. Herein, we realized the asymmetric chain-walking arylation of alkenyl alcohols for the construction of multisite tertiary and quaternary stereocenters in high yields and enantioselectivity. This new operation-friendly strategy carries substantial potential for future industrialization.