1. The acid, neutral and "intermediate" salts of calcium bilirubinate have been synthesized. 2. All are crystalline, and the intermediate salt which has 1 1/2 molecules of bilirubin per calcium atom probably has a crystal structure containing molecules of both acid and neutral salts. 3. The acid or intermediate salts have been found in 14 out of 70 gallstones analysed recently by X-ray diffraction.