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