A catalytic enantioselective nucleophilic aromatic substitution reaction which yields axially chiral biaryl derivatives in excellent yields with e.r. values of up to 97:3 has been developed. This process uses a chiral counterion to direct the addition of thiophenolate to a prochiral dichloropyrimidine by a tandem desymmetrization/kinetic resolution mechanism. The products can be derivatized to a range of atropisomeric structures without any reduction in enantioenrichment, thus offering access to unexplored chiral biaryl architectures. Asymm‐Desymm: A catalytic asymmetric nucleophilic aromatic substitution reaction which yields axially chiral biaryls in excellent yields with e.r. values of up to 97:3 has been developed. This process uses a chiral counterion to direct the addition of thiophenolate to an achiral dichloropyrimidine by a tandem desymmetrization/kinetic resolution mechanism. The products can be derivatized, thus offering access to unexplored chiral biaryl architectures.