The thermally activated release of the dielectric polarization of ZnF2:LiF crystals has been studied using the ionic thermoconductivity method. Measurements of the current discharge are made in single crystal samples oriented for polarization in the [001], [100], and [110] directions in order to study the crystallographic orientation dependence of the dielectric relaxation process. Strong discharge currents are observed only for [001]‐oriented crystals. The important parameters (including the activation energy, relaxation time, and number of dipoles) for the process are determined; the change in dipole orientation causing the discharge is examined in relation to possible anion vacancy movements in the lithium‐doped zinc fluoride crystal structure. The results confirm that the dielectric relaxation of lithium‐doped ZnF2is dependent upon the crystallographic orientation of the dielectric material.