The economic impact of catalysis is significant contributing 30–40% of global GDP. In this context, phase-transfer catalysis is a powerful manifold for asymmetric synthesis. Chiral cationic or anionic PTC strategies have enabled a variety of transformations, yet studies on the use of insoluble inorganic salts as nucleophiles for the synthesis of enantioenriched molecules have remained elusive. A long-standing challenge is the development of methods for asymmetric carbon–fluorine bond formation from cost-effective alkali metal fluorides. In this lecture, we will describe how hydrogen-bond donor catalysts can provide a solution to enantioselective nucleophilic fluorination through controlled fluoride binding.