A new type of intermolecular alkylative olefination of unactivated olefins and alkyl halides has been realized for the first time. This copper-promoted Heck-type reaction employs a directing-group strategy to efficiently produce the coupled alkyl olefin products with excellent regio- and stereoselectivity. A broad substrate scope including 1°, 2°, and 3° alkyl bromides and various nonactivated alkenes could be well tolerated. DFT calculations disclosed a dimethyl sulfoxide assisted concerted H-Br elimination process of a conformationally strained Cu(III) cyclic transition state.