An unprecedented N-heterocyclic carbene (NHC)-catalyzed enantioselective [3 + 2] annulation of enals with vinyl ketones has been achieved. Unlike chalcones, the β-unsubstituted enones, namely, vinyl ketones, have remained challenging in terms of reactivity, especially enantioselectivity. The disubstituted cyclopentenes were obtained in good yields and excellent stereoselectivities in the presence of Ti(OiPr)4.