Inspired by the ubiquitous prevalence of 3‐hydroxyoxindoles in natural products and pharmaceuticals, we herein disclose a direct and practical transition‐metal‐free asymmetric hydroxylation using commercially available Davis enantiopure oxaziridines as efficient oxidants, expeditiously affording an array of medicinally active 3‐functionalized 3‐hydroxy‐2‐oxindoles bearing quaternary stereocenters. The protocol features cheap reactants, ease of operation, scalability, and good functional‐group tolerance and efficient formal synthesis of natural products. [ABSTRACT FROM AUTHOR]