We are excited to present our newly developed method for the enantioselective oxidative coupling of C(sp 3 )-H bonds with various carboxylic acids using a cationic copper catalyst under blue light irradiation (Fig. ). This innovative approach addresses major limitations that have constrained the Kharasch reaction-a traditional method for oxidizing alkenes into allyl esters-for over six decades . While recent progress has been made in improving the enantioselectivity of the Kharasch reaction of cyclic alkenes , challenges remain, in particular the poor performance of open-chain alkenes and the limitations imposed by the use of peroxy esters as oxygen nucleophiles. By utilizing open-chain alkenes and alkynes, our method greatly expands the reaction's scope. More significantly, our method employs carboxylic acids instead of peroxy esters as oxygen nucleophiles, thus endowing the C(sp 3 )-H bond oxidation reaction practical. Furthermore, we have identified Cu III intermediates in this reaction using electron paramagnetic resonance. Traditionally, only Cu I and Cu II states have been observed in catalytic cycles; the identification of high oxidation states such as Cu III adds an essential dimension to our understanding of coppercatalyzed oxidation reactions.