A multicomponent organocatalyzedhighlydiastereo- and enantioselective synthesis of CF(3)-substituted aziridines is described. This reaction of in situ generated CF(3)CHN(2) and aldimines was realized by chiral Bronsted acid catalysis. The utility of the products is illustrated by easy access to beta-CF(3) isocysteine and aziridine-containing dipeptides.