The disclosure relates to an enzymatic esterification process for obtaining 17(-monoesters of cortexolone represented by formula (I) and its 9,11-dehydro derivatives starting from the corresponding 17(,21-diesters which comprises an enzymatic alcoholysis reaction in presence of a lipase from Candida. Furthermore, the disclosure relates to crystalline forms of cortexolone 17(-propionate to give cortexolone-17and 9,11-dehydro-cortexolone 17(-butanoate, for example by crystallizing said cortexolone-17(-propionate from a mixture of dichloromethane/n-hexane, or a mixture of acetone/n-hexane, or a mixture of ethanol/water, to get the crystalline form (III).
