Abstract Herein, a three component Catellani‐type reaction catalyzed by the Palladium/Norbornene/CuI (Pd/NBE/CuI) cooperative system by using N ‐acylph‐thalimides as acyl electrophiles is reported, which gives access to a series of aromatic ketones. The transformation is performable in the presence of water, albeit with decreased reaction yield. The additive CuI was crucial to facilitate the cleavage of C(O)−N bond of imide. This protocol showed broad substrate scope: both alkyl and aryl acyl groups could be installed at the ortho ‐position of aryl iodides; alkenes and boronic acids can be used as termination reagents. magnified image