AbstractParticle induced X‐ray emission (PIXE) analysis is generally accepted to be a depth insensitive technique and most of the work up until recently has been oriented to the analysis of in‐depth homogeneous samples. Up until recently, multilayer targets were normally looked upon as a source of problems, implying a limitation to qualitative or semi‐quantitative approaches. The growing need to analyse layered targets having complex structures or close Z elements, which provide unsolvable Rutherford backscattering spectrometry (RBS) spectra, pointed out the need to change this situation. The coupling of two software codes, namely NDF and DATTPIXE, was thus carried out a few years ago based on the development of a PIXE yields simulation library, LibCPIXE. Since then, developments were introduced at various levels, from the software code level to the level of analytical methodologies and even equipment. Starting in the concepts of equivalent depth and differential PIXE, and ending in the possibilities opened up by the use of microcalorimeter high‐resolution detectors within this context, an overview of the current status of development of the analytical technology involved is made. Copyright © 2011 John Wiley & Sons, Ltd.