A new catalyst system for the synthesis of R-aryl-substituted nitriles is reported. The bicyclic triaminophosphine P(i-BuNCH2CH2)3N (1b) serves as an efficient and versatile ligand for the palladium-catalyzed direct R-arylation of nitriles with aryl bromides. Using ligand 1b, ethyl cyanoacetate and primary as well as secondary nitriles are efficiently coupled with a wide variety of aryl bromides possessing electron-rich, electron-poor, electron-neutral, and sterically hindered groups.