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An enantioselective deoxygenative cyanation of benzyl alcohols was accomplished for the first time through the synergistic photoredox and copper catalysis.This reaction features the use of organic photosensitizer and low-cost 3d metal catalyst,simple and safe operations,and extremely mild conditions.A variety of chiral benzyl nitriles were produced in generally good yields and high level of enantio-controls from readily available feedstocks(22 examples,up to 93％ yield and 92％ ee).