The enantioselective addition of anilines to azoalkenes, was accomplished through the use of a chiral phosphoric acid catalyst. The resulting alpha-arylamino hydrazones were obtained in good yields and excellent enantioselectivities and provide access to enantioenriched alpha-arylamino ketones. A serendipitous kinetic resolution of racemic alpha-arylamino hydrazones is also described.