The cobalt-catalyzed aza-NHK (Nozaki–Hiyama–Kishi) reaction of ketimine has been realized to access diverse α-tertiary vinylic amino esters with excellent enantioselectivity and broad functional group tolerance. Notably, both configuration of alkenyl halide provides the same stereochemical outcome of chiral α-alkenyl quaternary amino ester, indicating that isomerization of alkenyl fragment might be