Carboranyl amines are distinct from typical organic amines. Due to the electronic influence of the carborane cage, they have low nucleophilicity and are reluctant to alkylate. Moreover, asymmetric synthesis of chiral carboranes is still in its infancy. Herein we have achieved the first catalytic asymmetric N-alkylation of o-carboranyl amine, providing general access to diverse secondary o-carboranyl amines with high efficiency and enantioselectivity under mild conditions. For the first time, asymmetric organocatalysis was introduced to carborane chemistry. Key to the success is the use of in situ generated (naphtho-)quinone methides as the alkylating reagents and suitable chiral acid catalysts. This protocol is also applicable to the asymmetric S-alkylation of 1-SH-o-C2B10H11. Control experiments and kinetic studies provided important insights into the reaction mechanism, which likely involves rate-determining generation of the quinone methide followed by fast and enantio-determining nucleophilic addition.