Using selected models and appropriate NMR techniques, it has been demonstrated that dehydroxyfluorination in the propargylic position can be highly regio- and stereoselective. The corresponding propargylic fluorides are very useful intermediates for short preparations of stereodefined unsaturated or polyunsaturated compounds with a single fluorine atom in allylic or propargylic position. This strategy offers good means for the synthesis of chiral, nonracemic monofluorinated analogues of natural products.