The invention is a UF.sub.6 -recovery process of the kind in which a stream of substantially pure gaseous UF.sub.6 is directed through an externally chilled desublimer to convert the UF.sub.6 directly to an annular solid ring adhering to the interior wall of the desublimer. After accumulation of a desired amount of solid UF.sub.6, the desublimer is heated to liquefy the solid. Subsequently, the liquid is recovered from the desublimer. It has been found that during the heating operation the desublimer is subjected to excessive mechanical stresses. In addition, it has been found that the incorporation of a very small percentage of relatively noncondensable, nonreactive gas (e.g., nitrogen) in the UF.sub.6 input to the desublimer effects significant decreases in the stresses generated during the subsequent melting operation. This modification to the process provides valuable advantages in terms of reduced hazard, lower operating costs for the desublimer, and increased service life for the desublimer and its auxiliaries. The new process is especially suitable for the recovery of enriched UF.sub.6 from high-speed UF.sub.6 gas-centrifuge cascades.