The Δ4-3-ketosteroids and α-ketolic steroids present in extracts prepared by five different procedures from urine have been examined by paper chromatography. The first extract, which consisted of those steroids extractable with chloroform at neutral pH contained cortisone and cortisol* and one to four unknown Δ4-3-ketosteroids. The second extract, representing steroids extractable immediately after acidification to pH 1 contained very little additional material. The third fraction consisted of extra steroids liberated after standing for 24 hr with acid; this rarely contained any detectable steroid material. A fraction which contained chloroform-soluble conjugated steroids was found to include small quantities of cortisone and cortisol and the other Δ4-3-ketosteroids. The final fraction contained large quantities of steroids liberated by hydrolysis with β-glucuronidase; these were mainly α-ketolic steroids including pregnane-3α: 17α: 21-triol-11: 20-dione, together with other unknown Δ4-3-ketosteroids. The distribution of the steroids in the various fractions is discussed and suggestions are made concerning the possible structure of some of the unknown steroids.