Enantiomerically pure 3'-fluorothalidomide (2) was successfully synthesized by enantiodivergent electrophilic fluorination using a combination of cinchona alkaloids and N-fluorobenzenesulfonimide (NFSI) as the key reaction. Importantly, a single chiral molecule, dihydroquinine (DHQ), allowed access to the mirror image form of 3'-fluorothalidimide by the choice of additives. While the use of TMEDA gave fluorinated (S)-4, the precursor of 2, with 78% ee, Cu(acac)(2)/bipy, afforded the antipode, (R)-4, in 77% ee.