We herein report a simple ether-directed iridium-catalyzed site- and enantioselective C(sp2)-H borylation of benzhydryl ethers for the first time. Various chiral benzhydryl ethers were obtained with high enantioselectivities in the presence of a tailor-made chiral bi-dentate boryl ligand. We found that the kinetic resolution relay significantly amplified the enantioselectivity. The synthetic utility of the current method was demonstrated by gram-scale C-H borylation and C-B bond transformations.