1,4-Benzodioxane widely exists as the core structure in many therapeutic agents and bioactive natural compounds. Hence, to access this kind of molecule, an enantioselective desymmetric C–O cross coupling reaction has been developed through dual visible light photoredox and nickel catalysis. Notably, the use of an axially chiral 2,2′-bipyridine ligand is the key to success. A series of chiral 1,4-benzodioxanes were afforded in high yields and moderate ...