Our research focused on the asymmetric C-H functionalization via metal-catalyzed radical relay pathway, where a diffusible carbon radical species formed by HAT could be trapped by a metal species to afford the C-H functionalized products. We aim to establish new mechanisms for radical-based C–H functionalization, enabling precise transformations of various C–H bonds of hydrocarbons and basic chemicals into high-valuable products. This research will provide transformative methods for the efficient synthesis of chiral molecules, offering new solutions for the production of fine chemicals, pharmaceutical intermediates, and functional materials.