We have utilized extended X-ray absorption fine structure (EXAFS) spectroscopy to investigate the site occupancy and local structure of Cr3+ and Cr6+ ions incorporated into electrodeposited alpha-Ni(OH)(2) films. The films were prepared by codeposition of Cr and Ni at constant cathodic current from aqueous solutions of nickel nitrate, chromium nitrate, and potassium chromate. EXAFS measurements show that in films produced from Ni2+ and Cr3+ solution, Cr3+ is incorporated into Ni lattice sites in alpha-Ni(OH)(2). On the other hand, cathodic codeposition of Cr6+ and Ni2+ results in CrO42- in interlamellar sites as well as sorbed on the surface of alpha-Ni(OH)(2). These results are of significance in a number of technological areas, e.g., batteries, corrosion protection, environmental speciation, and remediation. (C) 1999 The Electrochemical Society. S1099-0062(98)06-015-5. All rights reserved.