The use of aerosol defense sprays has increased as a means of self-defense and as a weapon in the commission of a crime. The residue of these sprays is often left behind as physical evidence on a victim's clothing or personal belongings. As the popularity of self-defense weaponry increases, so does the likelihood that it will be encountered in forensic casework. The extraction, recovery from fabrics, and identification of residue from defense sprays is described. The commonly used extraction method of liquid-liquid extraction is compared to solid phase microextraction (SPME) to recover capsaicin and dihydrocapsaicin from cotton swabs. The use of SPME resulted in lower limits of detection and greater recovery efficiency when compared to solvent extraction. SPME also provided more consistent recovery and less variability when compared to solvent extraction. The effect of use of various types of evidence packages on the preservation of this type of evidence is also reported. The collection and analysis of hand swabs after normal discharge of pepper spray canisters was studied indicating the low persistence of these compounds on the hands of the person conducting the spraying. Finally, the results of a real case whereby solvent-solvent extraction did not provide the necessary sensitivity for extracting the capsaicin compounds on the garments of a victim of an alleged spraying and the SPME extraction provided the recovery and identification of the compounds is also presented.