Abstract: The present invention relates to new esters of the 21-thiol-steroids, having the general formula given at (I) below, and also to a method of preparation of these new esters: ##STR1## in which: R.sub.1 represents an alkyl radical comprising a number of carbon atoms between 4 and 9, or a para-fluoro-aryl radical;R.sub.2 represents an atom of hydrogen or a methyl radical;R.sub.3 represents a hydroxyl radical of a ketone function;R.sub.4 represents an atom of hydrogen or an atom of fluorine;R.sub.5 and R.sub.6 each represent an atom of hydrogen or a second bond between the carbon atoms C-1 and C-2.A method of preparation of the above new esters comprises the operation of condensation of:Derivatives of the general formula below, in which R.sub.2, R.sub.3, R.sub.4, R.sub.5, R.sub.