A chiral Brønsted acid/Pd that cooperatively catalyzed the asymmetric cascade aza-Piancatelli rearrangement/ hydroamination of readily accessible alkynyl-functionalized tertiary furylcarbinols with anilines has been developed. This protocol provides expedient access to a variety of densely functionalized cyclopenta [b]pyrroline derivatives in high yields with excellent enantioselectivities.