Drug-facilitated sexual assault (DFSA) is a significant crime that is increasing in incidence. The employment of volatile substances such as chloroform and aromatic petroleum hydrocarbons in DFSAs is quite an unusual choice. The objective of this review is to explore the use of volatile substances in DFSAs. Using the PubMed database, a systematic review of the literature was conducted. Thereafter, citation searching was carried out within the included studies from the primary search. A total of five studies were eligible for inclusion. Chloroform was the drug used in the DFSA in three of the included studies, and aromatic hydrocarbons in the remaining two. Two of the offenders who employed chloroform possessed a unique way to access the drug: their degrees. The evidence found in the DFSA cases included a chloroform-scented scarf and a solvent-immersed cloth. Headspace gas chromatography-mass spectrometry, liquid chromatography-electrospray coupled tandem mass spectrometry, toxicology assays of blood and urine, and solvent or hydrocarbon gas chromatography flame-ionization detection followed by gas chromatography-mass spectrometry were among the investigations performed to detect the volatile substances. The implementation of stricter regulations on chloroform for employees in chemical industries and laboratories is recommended. In cases where the autopsy is unclear and there are conspicuous facial and airway injuries, it is prudent to collect an early sample for volatile substance analysis.