The three-dimensional structure of sheep liver 6-phosphogluconate dehydrogenase has been determined at 2.6 A resolution by X-ray crystallographic studies. The amino acid sequence of the enzyme is now known and can be fitted to a modified electron density map. Use of 6 A electron density maps and the results of chemical modification experiments allows description of the active site and identification of residues which may be implicated in the binding of co-enzyme and substrate.