Process for the recovery of hydrogen fluoride (HF) from a mixture, preferably an azeotropic mixture, of HF with water and/or an organic compound such as 134a, 125 or 133a, which comprises contacting the mixture with lithium fluoride or an alkaline earth metal fluoride to form a metal fluoride-hydrogen fluoride compound (e.g. lithium bifluoride, LiHF.sub.2), separating the compound and decomposing it to liberate hydrogen fluoride therefrom. The process is useful for recovering HF from azeotropic or azeotropic-like mixtures.