The local structure of interface or near interface impurity elements has been observed by means of extended x-ray absorption fine structure spectroscopy (EXAFS). Multilayered samples were prepared using reactive ion sputtering, electron beam evaporation , and molecular beam deposition methods with vacuum conditions ranging from 10−5 to 10−9 Pa. The interface layers of titanium, gallium, and arsenic were deposited in partial to multiple atom layers alternating with 5 to 10 nm thick matrix layers of nickel, cobalt, or aluminum. Oxide phases, atoms in solution, and local ordering were identified. Ti oxides and silicon arsenide were used as standards for the EXAFS analysis. Auger electron spectroscopy complemented the EXAFS analysis.