Gunshot residue (GSR) is typically found on the hands or clothing of persons who have been in the environment of a discharging firearm, but it may also be found on objects in the vicinity of the discharge. Computer-controlled scanning electron microscopy (CCSEM) is the method preferred by the forensic community for the automated analysis of GSR. GSR samples are therefore typically collected from a crime suspect's hands and/or clothing using SEM sample stubs coated with a conductive adhesive. The three major components in modern firearm cartridge primers are lead styphanate (initiator), antimony sulfide (fuel), and barium nitrate (oxidizer). GSR consists of the products of combustion of these primer materials. Large populations of particles in the size range of ~1–10 μm are rapidly screened by energy-dispersive X-ray spectroscopy (EDS) for the presence of combinations of Pb, Sb, and Ba. When combinations of these three elements are detected, the particles are flagged as potential GSR particulate. Flagged particles with significant Pb/Sb/Ba compositions are subsequently relocated for a live identification and a positive confirmation of GSR. Positive particles are classified as being either “characteristic of GSR” (that is, all three key elements are present) or “consistent with GSR” (that is, any two of the key elements are present) based on the particle composition and morphology. Classification is based on the presence of the constituent elements and is not dependant on the element amounts. If a particle does not meet the proper compositional or morphological criteria, it is rejected as GSR. However, CCSEM generally does not provide information regarding the population of particles much less than 1 μm or the surface chemistry of the GSR particles. This article examines the fine fraction of GSR particles with high-resolution electron microscopy and complements the microscopy data with surface chemistry information from X-ray photoelectron spectroscopy (XPS).