Abstract: The present invention relates to a method of identifying ammunition type and/or weapon type used to fire the ammunition from gunshot residue. This method involves providing a sample including a gunshot residue, subjecting the sample to spectroscopic analysis to produce a spectroscopic signature for the sample, and identifying the spectroscopic signature to ascertain the type of ammunition and/or the type of weapon used to fire the ammunition. A method of establishing reference spectroscopic signatures for ammunition type and/or weapon type used to fire the ammunition is also disclosed.