We have utilized “in situ” X-ray Absorption Fine Structure Spectroscopy to investigate the structure and composition of thin oxide films of nickel and iron that have been prepared by electrodeposition on a graphite substrate from aqueous solutions. The films are generally disordered. Structural information has been obtained from the analysis of the data. We also present initial findings on the local structure of heavy metal ions, e.g. Sr and Ce, incorporated into the electrodeposited nickel oxide films. Our results are of importance in a number of technological applications, among them, batteries, fuel cells, electrochromic and ferroelectric materials, corrosion protection, as well as environmental speciation and remediation.