A new method for the determination of vertical concentration profiles and its application to bilayer diffusion couples are presented. The method combines sputter sectioning techniques withexsitutotal‐reflection x‐ray fluorescence (TXRF) analysis. It allows quantitative depth‐resolved analysis of alloys consisting of elements with atomic numbers ≥13, quantitatively and depth resolved. In contrast to other surface sensitive techniques like Auger electron spectrometry or secondary ion mass spectrometry, TXRF offers the advantage of determining the sampling depth with the same instrument, so that no assumptions about sputtering rates or auxiliary measurements are necessary. With this method a depth resolution of 2.5 nm is obtained, which is comparable with the best achievable results from other depth profiling methods. Moreover, an additional TXRF scan in a nondestructive mode of operation makes a mutual comparison with the results of the sectioning technique possible. ©1995 American Institute of Physics.