A palladium‐catalyzed four‐component carbonylative coupling reaction involving aryl halides, internal alkynes, arylboronic acids, and CO has been developed for the first time. All‐carbon substituted α‐unsaturated ketones and benzofulvenes can be selectively obtained in a highly regio‐ and stereocontrolled manner. Using Cu(TFA)2 as the additive, a series of tetrasubstituted α‐unsaturated ketones were