Fluorosulfuric acid esters can be produced by reacting alcohols with sulfuryl fluoride (SO
2
F
2
) in the presence of a base and water. As a substrate thereof, optically active secondary alcohols are preferable, and optically active α-hydroxyesters and optically active 4-hydroxyprolines are particularly preferable. By performing the reaction in a two-phase system in the presence of a reaction solvent immiscible with water, a desired reaction proceeds particularly well. The present invention is a production method solving all the problems involved in conventional techniques while being industrially practicable.