Herein, we disclose the N‐heterocyclic carbene (NHC)‐catalyzed 3+3] annulation of challenging esters with methyl ketoimines for the highly enantioselective synthesis of intriguing δ‐lactams featuring various substituent patterns. The annulation occurs under mild conditions and offers good tolerance, good yields and excellent enantioselectivities. The six‐membered heterocyclic products are valuable for the synthesis of bioactive molecules.