In modem technology, thin films are shrinking more and more to a thickness of few nanometers. Analytical investigations of such thin films using the traditional sputter depth profiling, sputtering in combination with surface-analytical techniques, have limitations due to physical effects especially for very thin films. These limitations are pointed out and some alternatives are discussed. Non-destructive analysis with angle-resolved X-ray photoelectron spectroscopy is demonstrated to be a useful method for such investigations. Both qualitative and quantitative results can be obtained even for complex layer structures. Nevertheless, there are also limitations of this method and some alternatives or complementary methods are considered. (c) 2005 Elsevier B.V. All rights reserved.