3 alpha-Hydroxy-17-acetoxy-6 alpha-methyl-5 beta-pregnan-20-one (IIIa) has been isolated from urine of patients receiving medroxyprogesterone acetate (MPA). It was characterized by partial synthesis from MPA by catalytic reduction with palladium-charcoal to 17-acetoxy-6 alpha-methyl-5 beta-pregnan-3,20-dione (IV) and reduction of the latter with sodium borohydride. The isolation of 6 beta, 17,21-trihydroxy-6 alpha-methyl-pregn-4-ene-3,20-dione (IIc) is reported for the first time. The 17- and 21-monoacetates of this compound have been isolated and characterized earlier by other investigators. 7 alpha-3H-Medroxyprogesterone acetate was administered to 4 subjects by intravenous and intramuscular injections and by mouth. The ring A saturated metabolite IIIa was excreted in 0.1% to 4.0% of the administered dose; the highest excretion was after the intravenous dose and lowest after oral ingestion. 6 beta, 17,21-Trihydroxy-6 alpha-methylpregn-4-ene-3,20-dione (IIc) and its 17- and 21-monoacetates were excreted in about 5% of the doses in all subjects. No increase in 6 beta-hydroxylation was observed in the patient treated with o,p'-DDD,2,2-bis(2-chlorophenyl, 4'-chlorophenyl)-l,1-dichloroethane.