A process for the preparation of a 5-halo-6,9.alpha.-oxido-prostaglandin derivative of the formula ##STR10## wherein R.sup.1 is hydrogen, C.sub.1 to C.sub.2 straight or branched alkyl which can be substituted with amino, hydroxyl or halogen, a pharmaceutically acceptable organic or inorganic cation or a hydroxyl protecting group selected from the group which consists of tetrahydro pyranyl, alkylsilyl, aromatic or aliphatic acyl or aromatic carbamoyl eliminated by hydrolysis;
- R.sup.2 is hydrogen hydroxyl or hydroxyl having a hydroxyl protecting group selected from the group which consists of tetrahydro pyranyl, alkylsilyl, aromatic or aliphatic acyl or aromatic carbamoyl eliminated by hydrolysis;
- R.sup.3 is hydrogen or lower alkyl;
- R.sup.4 is hydrogen or a hydroxyl protecting group selected from the group which consists of tetrahydro pyranyl, alkylsilyl, aromatic or aliphatic acyl or aromatic carbamoyl eliminated by hydrolysis;
- R.sup.5 is straight or branched chain C.sub.1 to C.sub.20 alkyl;
- and
- X is halogen,
- which comprises subjecting a prostaglandin F.sub.2.alpha. derivative of the formula ##STR11## to electrochemical oxidation in an aqueous medium containing ions selected from the group which consists of bromide and iodide.