Axially chiral five-membered heterobiaryls synthesized by enantioselective catalysis typically feature large ortho-substituents or a heteroatom in the chiral axis to maintain a stable configuration. Herein we report a cation-directed catalytic enantioselective desymmetrization method that enables rapid access to axially chiral imidazoles with the basic nitrogen at the ortho position and efficiently integrates π-stacking moieties to ensure a stable axial configuration for further applications. The process is operationally simple, is highly enantioselective, and can be performed on the gram scale. The majority of the products are obtained in >90% ee, but interestingly even those with only moderate ee can readily be enriched to near optical purity by selective racemate crystallization. Together with a mild phosphine oxide reduction method, axially chiral imidazoles such as StackPhos and its derivatives are readily prepared in high yield and excellent enantioselectivity on the gram scale. The method also enables the preparation of new chiral non-phosphine-bearing imidazoles.