Abstract: X-ray photoelectron spectroscopy (XPS) was used in the qualitative and quantitative analysis of explosive residues remained in an explosion case assisted with X-ray fluorescence spectroscopy (XRF) and scanning electronic microscopy energy dispersive X-ray analysis (SEM/EDX). It was judged that the explosive is pyrotechnic composition, which belongs to chlorate explosives. It was shown that by XRS the elemental composition and content of inorganic explosive residues could be detected non-destructively and quickly, and the chemical formula of the main explosive component could be determined. The determination of the type of explosives used by the criminal would provide clues for the investigation of explosion cases.