The grazing emission X-ray fluorescence (GEXRF) technique was applied to the analysis of different Al films, with nominal thicknesses in the range of 1 nm to 150 nm, on Si wafers. In GEXRF the sample volume from which the fluorescence intensity is detected is restricted to a near-surface region whose thickness can be tuned by varying the observation angle. This is possible because of the refraction of the fluorescence X-rays and the quite long emission paths within the probed sample. By recording the X-ray fluorescence signal for different shallow emission angles, defined relatively to the flat, smooth sample surface, the deposited Al surface layers of the different samples could be well characterized in terms of layer thickness, layer density, oxidation and surface roughness. The advantages offered by synchrotron radiation and the employed wavelength-dispersive detection setup were profited from. The GEXRF results retrieved were confirmed by complementary measurements. The experimental setup, the principles and advantages of GEXRF and the analysis of the recorded angular intensity profiles will be discussed in details.