The asymmetric denitrogenative cycloaddition has emerged as a powerful tool to build chiral aza-heterocyles. However, only one example of asymmetric denitrogenative cycloaddition of benzotriazole with unsaturated hydrocarbons has been explored so far, because the ring-opening of benzotriazole to generate α-imino metal carbenoid species is a thermodynamically unfavorable process. We herein report an efficient asymmetric denitrogenative cycloaddition of benzotriazoles with cyclic and acyclic 1,3-dienes enabled by Pd and chiral sulfonamide phosphine ligand. A variety of substituted hexahydrocarbazoles and indolines were delivered in good yields with high ee values. Interestingly, a pair of enantiomers could be obtained with the use of Xu1 and PC2 with the same absolute configuration. The synthetic utilities of the optically active hexahydrocarbazoles were also showcased.