The synthesis of a wide variety of α-amino amidine derivatives was accomplished through a one-pot three-component reaction from aromatic aldehydes, aromatic amines and isocyanides, catalyzed by bromodimethylsulfonium bromide (BDMS), in good yields. Some of the salient features of the present protocol are: mild reaction conditions, shorter reaction times, non-aqueous work-up procedure and no need for chromatographic separation.