It has been proved that time‐of‐flight secondary ion mass spectrometry (ToF‐SIMS) is a very effective technique enabling detection of traces of gunshot residues (GSRs) which are usually transferred from the palm (fingers) of an attendant of criminal scene on a primary base, e.g. top of table, glass and mobile phone. From the fingerprint, the GSRs are lifted by adhesive tape and analyzed on this secondary base by ToF‐SIMS. The results are images, in different ions, which reveal distribution of GSRs on the fingerprint. Scanning electron microscope‐energy dispersive spectroscopy (SEM‐EDS) is commonly used in examination of morphology and elemental composition of GSR particles. It was shown that ToF‐SIMS provides much additional relevant information which is important for forensic investigation. Copyright © 2012 John Wiley & Sons, Ltd.