The present invention refers to an enzymatic process for obtaining 17alpha-monoesters of cortexolone and/or its 9,11-dehydroderivatives starting from the corresponding 17alpha, 21-diesterswhich comprises an enzymatic alcoholysis reaction.Furthermore, the present invention refers to crystalline forms of cortexolone17alpha-propionate and 9,11-dehydro-cortexolone17alpha-butanoate.