3-Hydroxyoxindoles are common structural motifs found in a vast array of natural and biologically active molecules. Most catalytic methods for the asymmetric syntheses of these compounds require the use of transition-metal catalysts. In contrast, alternative catalytic procedures involving organocatalysis are scarce. Herein we disclose a novel aminooxygenation of oxindoles with nitrosobenzene catalyzed by a newly designed quinidine dimer to afford the desired products in good yields with enantioselectivities up to 96%. These reactions allow one to construct a C-O bond at the C(3) position of oxindoles with the creation of an oxygen-containing tetrasubstituted chiral center and provide a new, general organocatalytic approach to the synthesis of 3-hydroxyoxindole derivatives.