An Fe(III)-catalyzed expedient synthesis of 13-aryl-13H-indeno[1,2-l]phenanthrene is described by a double annulations of 2-alkynyl biaryls, initiated by the activation of acetal. This strategy provides a simple, efficient and regioselective synthesis of varieties of indenophenanthrene derivatives from easily available starting materials under mild conditions in high to excellent yields. A plausible reaction mechanism is proposed.