The first example of phosphine-catalyzed enantioselective [4 + 1] annulations between 2-enoylpyridine N-oxides and Morita-Baylis-Hillman carbonates is described. When 1,2-bis[(2 R,5 R)-2,5-dimethylphospholano]benzene monoxide is employed as organocatalyst, Morita-Baylis-Hillman carbonates react with 2-enoylpyridine N-oxides smoothly to afford a series of optically active 2,3-dihydrofurans in high yields (up to 96%) with excellent stereoselectivities (96 → 99% ee and >20:1 dr). Importantly, the method offers a facile synthetic approach to enantioenriched pyridine N-oxides featuring 2,3-dihydrofuran motifs.