11-Hydroxylated-steroids are prepared by subjecting 11-desoxy-steroids such as 11-desoxysterols, -bile acids, -cardiac oglycones, -saponins, and -sex hormones, which are saturated at the 11-position to the oxygenating activity produced by (a) a species of fungus of one of the genera Beauveria or Glomerella, e.g. G. cingulata, G. lagenarium and G. fusaroides, to form 11a -hydroxylated-steroids or (b) a species of the fungus of the genus Phoma to form a mixture of 11a - and 11b -hydroxylatedsteroids which may be separated by chromatography. Suitable reactants for use in the above process are 3-keto-11-desoxy-pregnanes and allopregnanes and unsaturated analogues thereof, and particularly 11-desoxy-steroids of the general formula <FORM:0915423/IV (b)/1> wherein R represents hydrogen or an acyl radical, R1 represents an a - or b - lower alkyl radical, and R2 represents an a - or b - hydrogen atom, and the corresponding 1-pregnenes, 4-pregnenes, 1,4-pregnadienes, and 1,4,6-pregnatrienes. In the case of a reactant containing a 21-acyloxy radical, simultaneous hydrolysis of the 21-acyloxy radical takes place to form a 21-hydroxy radical. Other reactants that may be used in the above process are 16-alkyl-5-pregnene-3b ,17a -diol and 3b ,21-diacetoxy-16a -methyl-5-pregnene-17a -ol-20-one and 16a -alkyl-5-pregnene-3b ,17a -diol-20-one. The process described above may also result in the formation of the corresponding 11,15-dihydroxy-15b -hydroxy-or 6b -hydroxy-steroid. Detailed examples are given in which the following by-products are also formed: 4-pregnene-6b , 17a ,21-triol-3,20-dione and 4-pregnene-15b , 17a ,21-triol-3,20-dione. 16a - Alkyl - 1,4-pregnadiene-17a ,21-diol-3,11, 20-trione is prepared by oxidising 16a -alkyl-allopregnane-11a ,17a ,21-triol-3,20-dione with chromium trioxide in pyridine to form 16a -alkyl-allopregnane-17a ,21-diol-3,11,20 - trione, 2,4-dihalogenating this compound and dehydrohalogenating the resulting 2,4-dihalo compound, particularly the 2,4-dibromo compound. The product may then be further treated by acylating the 21-hydroxy group to form the corresponding 21-acylate. 16a - or 16b -Alkyl-11-desoxy-allopregnanes are prepared hydrogenating 16(a or b )-alkyl-pregnenolone to form 16a or (b )-alkyl-allopregnane-3b -ol-20-one, converting this compound to the corresponding 20-enolacetate by refluxing with acetic anhydride and a strong acid such as p-toluenesulphonic or perchloric acid, treating the 20-enolacetate with a per-acid to form the corresponding 17,20-epoxide, hydrolysing the epoxide to form 16(a or b )-alkyl-allopregnane-3b ,17a -diol-20-one, brominating at C21 to form the corresponding 21-bromo compound, reacting the 21-bromo compound with, for example, sodium or potassium acylate to form the corresponding 21-acyloxy compound, oxidising the 21-acyloxy compound to form 16(a or b ) - alkyl - allopregnane-17a ,21 - diol-3,20-dione 21-acylate, and hydrolysing the 21-acylate to form the corresponding free 21-hydroxy compound. 16(a or b )-alkyl-1,4-pregnadiene-17a ,21-diol-3,20-dione is prepared by dihalogenating (particularly dibrominating) 16(a or b )-alkyl-allopregnane-17a ,21-diol-3,20-dione 21-acylate to form the corresponding 2,4-dihalo compound, dehydrobrominating the 2,4-dihalo compound to form 16(a or b )-alkyl-1,4-pregnadiene-17a , 21-diol-3,20-dione 21-acylate, and hydrolysing the 21-acylate. 16b - alkyl-4-pregnene-17a ,21-diol-3,20-dione is prepared by epoxidising 16-alkyl-5,16-pregnadien-3b -ol-20-one to form the corresponding 16a ,17a -epoxy compound, acylating this compound to form 3b -acyloxy-16b -alkyl-16a , 17a -epoxy-5-pregnene-20-one, treating this compound with a hydrogen halide to form 3b - acyloxy - 16-methylene-5-pregnene-17a -ol-20-one, hydrogenating this compound to form 3b -acyloxy - 16b - alkyl-5-pregnene-17a -ol-20-one, 21-halogenating (particularly brominating) and reacting the resulting corresponding 21-halo compound with sodium or potassium acylate to form 3b ,21-diacyloxy-16b -alkyl-5-pregnene-17a -ol-20-one, and either hydrolysing the diacyloxy compound to form the corresponding 3b ,17a ,21-triol, and oxidising the 3a -hydroxy group and rearranging the 5(6)-double to form a 4(5)-double bond by the action of acid, or treating the diacyloxy compound with a microorganism such as Flavobacterium dehydrogenane var. hydrolyticum. 16a -Alkyl-17a -hydroxy-4-pregnenes are prepared by halogenating (preferably chlorinating) 16a -alkyl-pregnenolone 3-acylate in a basic medium to form the corresponding 5,6-dihalo compound, 20-enol-acylating this compound with acetic anhydride and p-toluenesulphonic acid, treating the 20-enolacetate with a p per-acid to form a 17,20-epoxide, treating the 17,20-epoxide with alkali to form 16a - alkyl - 5,6-dihalopregnane-3b ,17a -diol-20-one 3-acetate, brominating this compound to form the corresponding C21-bromo compound, reacting the 21-bromo compound with sodium or potassium acetate to form 16a -alkyl-5,6-dihalo-pregnane-3b ,17a ,21-triol 21-acetate, oxidising and hydrolysing this compound with the microorganisms. Flavobacterium dehydrogenuns var. hydrolyticum to form 16a -alkyl-5,6-dihalo-pregnane-17a ,21-diol-3,20-dione, and dehalogenating this compound. Specifications 807,227, 843,211 and 843,217 are referred to.