Aryl substitute makes it different:A new general enantioselective hydrosilylation of N-aryl β-enamino esters with trichlorosilane has been developed (see scheme). The N-aryl substituent is crucial for the activity and enantioselectivity. In the presence of catalytic amount of readily accessible chiral N-picolinoylpyrrolidine derivatives, the reactions proceeded smoothly to provide various chiralβ-amino esters in good yields (≤97 %) and moderate to excellent enantioselectivities (≤96 % ee).