We report herein the first example of asymmetric hydroazidation of α-substituted vinyl ketones by using chiral primary amines as the catalysts.A simple chiral primary-tertiary diamine catalyst derived from lphenylalanine was found to readily promote this aza-Michael addition reaction with enamine protonation as the key stereogenic step,thus enabling the effective synthesis of α-chiral β-azido ketones with good yields and moderate enantioselectivities. We report here the first example of asymmetric hydroazidation of α-substituted vinyl ketones by using chiral primary amines as the catalysts. A simple chiral primary-tertiary diamine catalyst derived from lphenylalanine was found to be facile to this aza-Michael addition reaction with enamine protonation as the key stereogenic step, thus enabling the effective synthesis of α-chiral β-azido ketones with good yields and moderate enantioselectivities.