A new practical organocatalytic asymmetric protocol for the introduction of a monofluoroalkyl group into the oxindole framework has been successfully developed. Excellent diastereoselectivities (>20:1 dr) and enantioselectivities (93–99% ee) of the products were obtained with a wide range of pre-electrophiles (3-bromooxindoles) and prenucleophiles (α-fluorinated β-keto gem-diols). The obtained products themselves and their derivatives may significantly benefit drug discovery.