Grazing exit X-ray fluorescence (GE-XRF), which has unique advantages in surface and film analysis, is a development of XRF related to total reflection XRF. The combination of polycapillary X-ray optics with total reflection geometry in the detection path allows micro analysis in thin layer characterization. This technique was applied to analyze a series of titanium and iron layers which were deposited on GaAs single crystal by metal vapor vacuum arc ion sources. Thickness and density of the layers result from fitting the experimental data to model calculations, and the information of layer uniformity can be acquired by two-dimensional scan analysis. The GE-XRF method has application for complete layer characterization and process control during the layer deposition. (C) 2008 Published by Elsevier B.V.