Abstract Highly enantioselective α‐arylation of α‐amino acid derivatives via nucleophilic aromatic substitution (S N Ar) was achieved under phase‐transfer conditions. Various kinds of α‐amino acids and aryl triflates containing a nitro group can be tolerated in this reaction to give α,α‐disubstituted α‐amino acids in good to high enantioselectivity. This reaction demonstrates a valuable method for the catalytic asymmetric synthesis of α,α‐disubstituted α‐amino acids containing an aromatic substituent.