Abstract: The microstructure and chemical compositions of pyrotechnic compositions and pyrotechnic explosive residues were studied by scanning electron microscope (SEM) and X-ray energy dispersive spectroscopy (EDS). The pyrotechnic explosive residues particles collected from the surface of the reaction region were observed. The majority of pyrotechnic explosive residues particles had a regular morphology of spherical shape, their diameter ranging from about 40 to 100 μm. Their main components were carbon and alumina. The amounts of aluminum oxide in different kinds of pyrotechnic explosion residues were different and the average diameter of these spherical particles was also different. These remarkable features were helpful to identify pyrotechnic composition simply, rapidly and accurately, and it provided a powerful scientific evidence for the pyrotechnic explosion scene detection work.