Fluoride compounds through ingestion, inhalation or skin contact hydrolyze to fluoride ion and form corrosive hydrofluoric acid on the mucosa, and also act as a direct cellular poison which interferes with calcium metabolism and enzyme mechanisms to induce hyperkalemia and hypocalcemia, following to dysrhythmias and cardiac arrest. Although fluoride compound is very important substance in forensic science, it is one of the substances that are difficult to be identified by a routine toxicological analysis among all chemicals in the forensic case caused by "unknown" substance or a workplace chemical accident. Identification of fluoride compound often goes beyond the general analytical procedure, so a more systematic procedure should be suggested. This study reviews the analytical results of fluoride compound-related accident cases submitted to the National Forensic Service and presents improved analytical plans. In the case reviewed, hydrogen fluoride, sodium fluoride, ammonium fluoride, sodium fluorosilicate, calcium fluoride, nitrogen trifluoride were identified. These six types of fluoride compounds are suggested as accident preparedness substances that should be considered in forensic analysis of hazardous chemical accident in Korea.