With electronically unbiased styrenes and indenes as dienophiles, a highly enantioselective all-carbon-based inverseelectron-demand Diels−Alder reaction of electron-deficient 2-pyrones is reported. Using C 1 -symmetric imidazolidinepyrroloimidazolone pyridine as the tridentate ligand and Ni(OTf) 2 as the Lewis acid, diverse bridged bicyclic lactones were obtained in high yields (88−97% yields), diastereoselectivities (>95:5 dr), and enantioselectivities (90−99% ee). Cyclic enamine and 2,3-dihydrofuran were also suitable dienophiles. DFT calculations supported a concerted [4 + 2] cycloaddition mechanism for the Ni(II) complex-catalyzed reaction with high enantioselectivity caused by steric factors.