This study introduces a novel approach to enantioselective aziridination of unactivated terminal alkenes using a planar chiral rhodium indenyl catalyst. The method demonstrates excellent functional group tolerance and chemoselectivity, favoring unactivated alkenes over activated ones. Computational studies reveal a stepwise mechanism involving alkene migratory insertion, which is both the enantio- and rate-determining step. The catalyst's enantioselectivity is attributed to steric interactions between the substrate and the catalyst's indenyl ligand. This work expands the scope of enantioselective aziridination reactions and highlights the potential of the planar chiral indenyl catalyst as a versatile platform for further development.This study introduces a novel approach to enantioselective aziridination of unactivated terminal alkenes using a planar chiral rhodium indenyl catalyst. The method demonstrates excellent functional group tolerance and chemoselectivity, favoring unactivated alkenes over activated ones. Computational studies reveal a stepwise mechanism involving alkene migratory insertion, which is both the enantio- and rate-determining step. The catalyst's enantioselectivity is attributed to steric interactions between the substrate and the catalyst's indenyl ligand. This work expands the scope of enantioselective aziridination reactions and highlights the potential of the planar chiral indenyl catalyst as a versatile platform for further development.