The toxic Paraphenylenediamine is characterized by infrared spectrophotometry and nuclear magnetic resonance spectroscopy, whereas, high performance liquid chromatography with a refractive index detector was used to determine its purity in the suspect samples using external standardisation. An analytical method for determination of lower traces of paraphenylenediamine in post-mortem biological fluids was developed. This procedure involves deproteneization or hydrolysis followed by liquid-liquid extraction and derivatization with trifluoroacetic anhydride. 1 microL of the extract was then analysed by gas chromatography/iontrap mass spectrometry. Benzidine used as the internal standard for quantification and the extraction recovery test was evaluated to 85%. This method was validated in cases with paraphenylenediamine poisoning.