The purpose of this review is to introduce current trends and future directions in efforts to obtain 3D images of materials both destructively and non-destructively by means of X-ray photoelectron spectroscopy. Non-destructive methods for creating a 3D volume of the material include peak shape analysis, image fusion of angle-resolved images, combination of ARXPS and mapping and multivariate analysis of ARXPS data. Destructive sputtering of nanocomposite samples with ion beams followed by analysis with X-ray photoelectron spectroscopy represents a powerful strategy for in-depth characterization of complex materials. The combination of photoelectron imaging with depth profiling to create 3D images is essential for accurate structure determination of laterally and vertically heterogeneous materials. There are only a few reports in the scientific literature, however, describing this approach. Advances towards realization of these experiments with assistance of multivariate analysis will be discussed. (C) 2009 Elsevier B.V. All rights reserved.