A palladium-catalyzed tandem reaction of 2-(quinazolinone-3(4H)-yl)benzonitriles with arylboronic acids has been developed, allowing access to a new class of 2-(4-arylquinazolin-2-yl)anilines that were often difficult to prepare using previous methods. In particular, the newly produced amino group is amenable to further synthetic elaborations, thereby broadening the diversity of the products. The structure of the newly synthesized 2-(4-arylquinazolin-2-yl)anilines was unambiguously confirmed by X-ray crystallography. Moreover, a possible mechanism for the formation of 2-(4-arylquinazolin-2-yl)anilines is discussed.