Chiral anion phase-transfer catalysis has enabled the direct and highly enantioselective fluorinative dearomatization of phenols catalyzed by a BINOL-derived phosphate. The process efficiently transforms simple, readily available phenols into fluorinated chiral small molecules bearing reactive functionality under ambient reaction conditions with high enantioselectivity. The close relationship of the products with well-studied o-quinols provides numerous avenues for synthetic elaboration and exciting opportunities for bioisosteric replacement of hydroxyl with fluorine in natural products.