An unprecedented asymmetric acyl-carbamoylation of pendant alkenes tethered on aryl carbamic chlorides with both aliphatic and aromatic aldehydes has been developed via the cooperative catalysis of a chiral nickel-PHOX complex and tetrabutylammonium decatungstate. This reaction represents the first example of merging hydrogen-atom-transfer photochemistry and asymmetric transition metal catalysis in difunctionalization of alkenes. Using this protocol, a variety of oxindoles bearing a challenging quaternary stereogenic center are furnished under mild conditions in highly enantioselective manner.