Trace amounts of explosives were detected on human nail using confocal Raman microscopy. Contamination of the nail can result from the manual handling, packaging or transportation of explosive substances. Raman spectra were obtained from pentaerythritol tetranitrate (PETN), trinitrotoluene (TNT), ammonium nitrate and hexamethylenetetramine (HMTA) particles on the surface of the nail with dimensions in the range 5–10 µm. An added difficulty in an analytical procedure is the presence of a nail varnish coating that has been applied, which traps the particulate matter between the coating and nail. Using confocal Raman microscopy, interference‐free spectra could be acquired from particles of explosives visually masked by the nail varnish. Spectra of the explosives could be readily obtained in situ within 90 s without alteration of the evidential material. Acquisition of a Raman point map of a PETN particle under the nail varnish coating is also reported.