Sputter depth profiling is commonly used to obtain valuable information regarding the three dimensional distribution of elements within a sample, and is one of the best ways to measure the composition of a buried interface or the uniformity of a thin film. X-ray photoelectron spectroscopy (XPS) is one of the analysis tools often used in conjunction with ion beam erosion to obtain sputter depth profiles. However, to obtain accurate depth information it is often necessary to understand better the sputtering process for a specific materials system. Artifacts such as differential sputtering, varying sputter rates and ion beam-induced chemistry are well known. Here, however, we present evidence from experiments on a porous thin film deposited on an Si wafer that relatively small chemical and/or structural changes in a nanoporous film can affect the rate of erosion measured during sputter depth profiling. Reproducible variations in sputter rate are found with chemical modification leading to compositional changes of the nanoporous thin film. The origin of the sputter rate changes is discussed with the aid of results obtained using Fourier transform infrared spectroscopy, profilometry, nuclear reaction analysis, electron microscopy and XPS-based depth profiling. Copyright © 2005 John Wiley & Sons, Ltd.