The present invention refers to an enzymatic process for obtaining 17.alpha.monoesters of cortexolone and/or its 9,11-dehydroderivatives starting from the corresponding 17.alpha., 21-diesters which comprises an enzymatic alcoholysis reaction. Furthermore, the present invention refers to crystalline forms of cortexolone 17.alpha.-propionate and 9,11-dehydro-cortexolone 17.alpha.-butanoate.
