A facile and straightforward synthesis of benzoimidazo[2,1-a]isoquinolines through Ru(II)catalyzed [4 + 2] annulation reaction of 2-aryl benzimidazole and styrene has been explored. Tentative mechanistic studies imply the current reaction involves sequential CÀC/CÀN bond formation through the ortho CÀH activation of 2-aryl benzimidazole followed by CÀN reductive elimination. This newly developed strategy is widely applicable and tolerates various 2-arylbenzimidazole and vinyl derivatives, and allows the attractive vehicle for direct construction of diverse C6-substituated benzoimidazoisoquinoline scaffold in good yields.