The first highly enantioselective decarboxylative addition of 尾-ketoacids to isatins mediated by a bifunctional tertiary amine鈥搕hiourea catalyst has been developed, allowing facile synthesis of biologically important 3-hydroxy oxindoles in good yields and excellent enantioselectivities. The method reported represents a valuable approach of utilizing 尾-ketoacids as synthetic equivalents of aryl/alkyl methyl ketone enolates.