Raw materials, intermediates and subsidiary colours in Food Yellow No. 5 (Sunset Yellow FCF) were determined using liquid chromatography/mass spectrometry (LC/MS) with electrospray ionization. A gradient consisting of acetonitrile and 0.04% aqueous ammonium carbonate solution was used for the HPL C mobile phase. Quasi-molecular ions of impurities were used as monitor ions. It was necessary to use fragment ions of the sodium salts of 6-hydroxy-5-phenylazo-2-naphthalenesulphonic acid (SS-AN) and 4-(2- hydroxy-1- naphthylazo) benzenesulphonic acid (2N-SA) as monitor ions because the compounds are not resolved by chromatography and have the same molecular weight. Fifteen samples of commercial Sunset Yellow FCF were examined. The results obtained by UV-Vis spectroscopy were in good agreement with the results of LC/MS analyses. The detection limits of the impurities in Sunset Yellow FCF ranged from 0.01 to 0.1%.