A novel copper/manganese cocatalyzed direct oxidative coupling of terminal vinylarenes with ketones via C(sp3)鈥揌 bond functionalization following C鈥揅 bond formation has been developed using tert-butyl hydroperoxide as the radical initiator. Various ketones underwent a free-radical addition of terminal vinylarenes to give the corresponding 1,4-dicarbonyl products with excellent regioselectivity and efficiency through one step. A possible reaction mechanism has been proposed.