A rapid approach for the nondestructive, accurate detection of organic gunshot residue was investigated. Raman microscopy was used to identify organic gunshot residue and the propellant in ammunition. The optimal excitation wavelength for the detection of organic particles using Raman spectroscopy was 473 nm. The Raman spectra of organic gunshot residue obtained using 473 nm laser excitation can effectively avoid the interference of fluorescence. The results demonstrated that the organic particles were mainly from the partially burned propellant particles. Meanwhile it was proved that the main component was basically consistent with the propellant except somehow damage in chemical structure or degree of crystallization with Raman spectra. The surface color of organic particles was mainly brassiness, dark gray. A lot of craters were distributed on the surface of organic particles. Spherical inorganic particles with metallic luster attached to the surface of organic particles can be regarded as the typical characteristics of gunshot residue.