A rare fatal case of self-poisoning with nitrobenzene following oral ingestion is reported. On presentation to the hospital, severe methemoglobinemia (70%) was observed in an 82-year-old male who had ingested 250 mL of an unknown substance in the previous 24 h. Methylene blue and exchange transfusion were the therapeutic methods applied in the treatment of the methemoglobinemia. Forty-eight hours after ingestion, a blood sample was collected in ICU and sent to our laboratory. We detected that the blood contained 3.2 microg/mL of nitrobenzene. The determination of nitrobenzene was performed using the combination of GC-FID for screening analysis and quantitation and GC-MS for confirmation of the obtained results.